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    • 专利摘要:
    the present invention relates to a method for the preparation of compounds having a 6-oxabicyclo[10.3.1]pentadecenoic structure, especially of 14-methyl-16-oxabicyclo[10.3.1]pentadecenes, and the subsequent products thereof.
    公开号:BR112018010389B1
    申请号:R112018010389-6
    申请日:2016-11-22
    公开日:2022-01-18
    发明作者:Albert Werner；Mirian Bru Roig；Joaquim Henrique Teles；Stefan RUEDENAUER；Stefan Maurer；Manuel Danz
    申请人:Basf Se；
    IPC主号:
    专利说明:

    FUNDAMENTALS OF THE INVENTION
    [001] The present invention relates to a method for preparing compounds having a skeleton of 16-oxa-bicyclo[10.3.1]pentadecene, especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene, and products of conversion thereof. PREVIOUS TECHNIQUE
    [002] Macrocyclic ketones with 14- to 18-membered rings, for example, cyclopentadecanone (exaltone), 3-methylcyclopentadecanone (muscone) and 3-methylcyclopentadecenone (dehydromusone or Muscenone®), are desirable fragrance or aroma substances whose synthetic preparation was and is the subject of extensive investigations. In particular, the non-naturally occurring mixture of 3-methylcyclopentadec-4-en-1-one and 3-methylcyclopentadec-5-en-1-one is of particular interest because of its olfactory properties. This mixture of 3-methylcyclopentadec-4-en-1-one and 3-methylcyclopentadec-5-en-1-one is referred to below as "dehydromuscone". Formula (A) below, where the symbol is in one case a single bond and in one case a double bond, shows dehydromuscone without regard to positional and double bond isomers. Formulas (A') and (A'') show the two double bond isomers without considering the cis-trans isomers of the double bonds. Copy formulas (A) (A') (A'')

    [003] In the context of the invention, structure (A) includes the pure compound (A'), the pure compound (A'') and any mixtures of (A') and (A"), where the double bonds can each a ter or a cis or trans geometry.
    [004] The synthesis of dehydromusone is described, inter alia, in the following documents: US 3,778,483; US 4,480,107 and CH 513791.
    [005] The isomers of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (D) are important intermediates in the preparation of dehydromusone (A) and muscone. For example, a three-stage synthesis of dehydromusone (A) may start from 3-methylcyclopentadecane-1,5-dione (B) and may comprise the following steps:
    1. Reduction of 3-methylcyclopentadecane-1,5-dione (B) to 3-methylcyclopentadecane-1,5-diol (C).
    [006] 2. Catalytic dehydrogenation and dehydration of 3-methylcyclopentadecane-1,5-diol (C) to 14-methyl-16-oxabicyclo[10.3.1]pentadecene (D).
    [007] 3. Conversion of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (D) to dehydromuscone (A).
    [008] In step 2), 3-methylcyclopentadecane-1,5-dione (B) and 14-methyl-16-oxabicyclo[10.3.1]hexadecane (E) can occur as by-products. Furthermore, during the conversion of 3-methylcyclopentadecane-1,5-diol (C) to 14-methyl-16-oxabicyclo[10.3.1]pentadecene (D), 3-methylcyclopentadecan-5-ol-1-one (F ) can be formed as an intermediary:

    [009] US 4,335,262 describes, inter alia, the preparation of dehydromuscone (A) by dehydrogenation and dehydration of 3-methylcyclopentadecane-1,5-diol (C) to give 14-methyl-16-oxabicyclo[10.3.1 ] pentadecene (D) using Raney copper in batch mode (Example 4 from US 4,335,262). In this case, 14-methyl-16-oxabicyclo[10.3.1]pentadecene is separated from the reaction mixture directly by distillation. Subsequently, 14-methyl-16-oxabicyclo[10.3.1]pentadecene can be subjected to a reaction with phosphoric acid in toluene to obtain dehydromuscone (A) (Example 5 of US 4,335,262).
    [0010] A disadvantage of this method, however, is the low selectivity for dehydromuscone (A), since not considerable amounts of the saturated ether (E) are obtained, inter alia, which reduce both the yield and the purity of the product. target. Furthermore, the high viscosity of the reaction mixture makes the technical implementation of this method more difficult.
    [0011] The object of the present invention is to provide an improved method for the preparation of 16-oxabicyclo[10.3.1]pentadecenes, wherein the ring carbon 14 is unsubstituted or contains a C1-C4-alkyl residue. The synthesis must proceed, in this case, from the corresponding cyclopentadecane-1,5-diols. In particular, the object of the invention is to provide an improved method for the preparation of 14-methyl-16-oxabicyclo[10.3.1]pentadec-12-ene starting from 3-methylcyclopentadecane-1,5-diol. Here, 16-oxabicyclo[10.3.1]-pentadecene and especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene should be achieved with high conversion in good yield and purity.
    [0012] It has now been found that this objective is achieved by converting the corresponding clopentadecane-1,5-diol to the unsubstituted or substituted 16-oxabicyclo[10.3.1]pentadecene with C1-C4-alkyl over a dehydrogenation and dehydration catalyst and additionally in the presence of a high boiling solvent.
    [0013] Specifically, 16-oxa-bicyclo[10.3.1] pentadecenes that are unsubstituted or substituted with C1-C4-alkyl, such as 14-methyl-16-oxabicyclo[10.3.1]pentadecene, have been found to react in addition to unwanted saturated ether during an excessively long residence time in the reaction zone in contact with the catalyst and the hydrogen formed during the reaction. By adding a high boiling solvent according to the invention, it is possible to make the cyclopentadecane-1,5-diol starting material, for example 3-methylcyclopentadecane-1,5-diol, and the catalyst remains in the reaction zone, while the residence time of unsubstituted or C1-C4-alkyl-substituted 16-oxabicyclo[10.3.1]pentadecene in the reaction zone can be minimized. In this way, it is possible to obtain high yields, on the one hand, based on the cyclopentadecane-1,5-diol used and, at the same time, to improve the yield and purity of unsubstituted or substituted 16-oxabicyclo[10.3.1]pentadecene with C1-C4-alkyl. Furthermore, the mixing of the reaction mixture in the reaction zone can be improved by adding a high boiling solvent according to the invention (or the viscosity of the reaction mixture can be reduced).
    [0014] In particular, an apparatus is used to carry out the method according to the invention, which apparatus comprises a reaction zone and a distillation zone connected thereto. In particular, after the reaction starts in the reaction zone, a portion of the unsubstituted or substituted C1-C4-alkyl 16-oxabicyclo[10.3.1]pentadecene is in the distillation zone, even if 16-oxabicyclo[10.3.1 ]pentadecene unsubstituted or substituted with C1-C4-alkyl is taken therefrom. Also by means of this procedure, the residence time of the unsubstituted or substituted 16-oxabicyclo[10.3.1]pentadecene with C1-C4-alkyl in the reaction zone can be minimized and, consequently, its thermal stress.
    [0015] The method according to the invention is particularly suitable for the preparation of 14-methyl-16-oxabicyclo[10.3.1]pentadec-12-ene, starting from 3-methylcyclopentadecane-1,5-diol. In this specific embodiment, after the reaction starts in the reaction zone, a portion of the 14-methyl-16-oxabicyclo[10.3.1]pentadecene is in the distillation zone, even if no 14-methyl-16-oxabicyclo[10.3 .1]pentadecene is taken from it. SUMMARY OF THE INVENTION
    [0016] The invention relates to a method for preparing compounds of the general formula (I)
    where R1 is hydrogen or C1-C4-alkyl, and conversion products thereof, wherein a) a starting material is provided comprising a compound of the general formula (II)
    b) the starting material supplied in step a) is subjected in a reaction zone to a reaction at a temperature in the range of 100 to 240°C and at a pressure in the range of 0.01 to 15 kPa (0.1 at 150 mbar) in the presence of a heterogeneous catalyst and a solvent or a mixture of solvents having a vapor pressure between 1-5 and 10 kPa (10-5 and 100 mbar) at 180°C, and c) the compound of formula ( I) is separated from the reaction mixture by distillation.
    [0017] The invention further relates to a method in which d) compounds of the general formula (I) are subjected to a reaction to obtain at least one compound of the general formula (IV).
    where the symbol
    is in one case a single bond and in one case a double bond and R1 is hydrogen or C1-C4-alkyl.
    [0018] The invention further relates to a method in which e) compounds of the general formula (IV) are subjected to hydrogenation to obtain the compound of the general formula (V).
    where R1 is hydrogen or C1-C4-alkyl. FORMS OF CARRYING OUT THE INVENTION
    [0019] The method according to the invention comprises the following embodiments: 1. a method for preparing compounds of the general formula (I)
    where R1 is hydrogen or C1-C4-alkyl, and conversion products thereof, wherein a) a starting material is provided comprising a compound of the general formula (II)
    b) the starting material supplied in step a) is subjected in a reaction zone to a reaction at a temperature in the range of 100 to 240°C and at a pressure in the range of 0.01 to 15 kPa (0.1 at 150 mbar) in the presence of a heterogeneous catalyst and a solvent or a mixture of solvents having a vapor pressure in the range of 1-5 to 10 kPa (10-5 to 100 mbar) at 180°C and, c) the compound of formula (I) is separated from the reaction mixture by distillation.
    [0020] 2. The method according to embodiment 1, wherein R1 is hydrogen or methyl, particularly methyl.
    [0021] 3. The method according to embodiment 1 or 2, wherein the reaction in step b) comprises a first stage, during which the fraction not comprising any of the compounds of formula (I) is separated from the mixture of distillation reaction.
    [0022] 4. The method according to any of the preceding embodiments, wherein the separation of a fraction comprising the compound of formula (I) from the reaction zone by distillation in step c) is carried out in a phased manner or continuously.
    [0023] 5. The method according to any one of embodiments 1 to 4, wherein the vapor pressure of the solvent used in step b) is lower than the vapor pressure of the diol (II).
    [0024] 6. The method according to any one of embodiments 1 to 4, wherein the vapor pressure of the solvent used in step b) is between the vapor pressure of compound (I) and the vapor pressure of the compound (II).
    [0025] 7. The method according to any one of embodiments 1 to 4, wherein the vapor pressure of the solvent used in step b) is between the vapor pressure of compound (I) and the vapor pressure of the compound (III).
    where R1 is hydrogen or C1-C4-alkyl,
    [0026] 8. The method according to any of the preceding embodiments, wherein the solvent used in step b) is selected from - aliphatic, cycloaliphatic and aromatic hydrocarbons, - aliphatic, cycloaliphatic and monohydric and poly aromatic alcohols -hydrics, - ether alcohols, polyether polyols and mono- and dialkyl ethers thereof, aromatic ethers and open-chain aliphatic ethers, - ketones, - esters - mixtures thereof.
    [0027] 9. The method according to any of the preceding embodiments, wherein the solvent used in step b) is selected from -C10-C30-alkanes, -C6-C30-alkanols, -C2-C30-alkanediols , - polyalkylene glycols and mono- and dialkyl ethers thereof, - mixtures thereof.
    [0028] 10. The method according to any one of embodiments 1 to 9, wherein the separation in step c) is carried out by one-phase distillation.
    [0029] 11. The method according to embodiment 10 for the preparation of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1), wherein the compound of formula (I.1) is separated from the reaction mixture in step c) by a one-stage distillation and the separated product comprises the following compounds, based in each case on the total weight of the separated product: 14-methyl-16-oxabicyclo[10.3.1]pentadecene ( I.1): 75 - 95% by weight, 3-methylcyclopentadecane-1,5-diol (II.1): 0 - 5% by weight, 3-methylcyclopentadecane-1,5-dione (III.1): 1 - 10% by weight, 14-methyl-16-oxabicyclo[10.3.1]hexadecane (VI.1): 0-15% by weight.
    [0030] 12. The method according to any one of embodiments 1 to 9, wherein the separation in step c) comprises fractional distillation.
    [0031] 13. The method according to embodiment 12, wherein at least one distillation column, preferably a distillation column, having at least 10 theoretical plates is used for the distillation separation of a fraction comprising the compound of formula (I) in step c).
    [0032] 14. The method according to embodiment 12 or 13, wherein in distillation the ratio of the separated stream to the recirculated stream in the column is in the range of 1:1 to 1:30, and especially in the range of 1:1 to 1:20.
    [0033] 15. The method according to any one of embodiments 12 to 14 for the preparation of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1), wherein the compound of formula (I ) is separated from the reaction mixture in step c) by fractional distillation and the separated product comprises the following compounds, based in each case on the total weight of the separated product: - 14-methyl-16-oxabicyclo[10.3.1]pentadecene ( I.1): 80 - 99% by weight, - 3-methylcyclopentadecane-1,5-diol (II.1): 0 - 5% by weight, - 3-methylcyclopentadecane-1,5-dione (III.1) : 0 to 5% by weight, preferably 0 to 1% by weight, - 14-methyl-16-oxabicyclo[10.3.1]hexadecane (VI.1): 0 to 15% by weight, preferably 0 to 10% by weight, - solvent: 0 to 5% by weight, preferably 0 to 1% by weight, - 3-methylcyclopentadecan-5-ol-1-one (VII.1): 0-5% by weight .
    [0034] 16. The method according to any of the preceding embodiments, wherein the solvent content of the reaction mixture in step b) is always maintained at at least 20% by weight, preferably at least 30% by weight. weight, in particular at least 50% by weight, based on the total weight of the reaction mixture in the reaction zone.
    [0035] 17. The method according to any of the preceding embodiments, wherein a copper-containing catalyst, preferably Raney copper, is used as the catalyst in step b).
    [0036] 18. The method according to any of the foregoing embodiments, wherein d) the compounds of the general formula (I) are subjected to a reaction to obtain at least one compound of the general formula (IV)
    where the symbol
    is in one case a single bond and in one case a double bond and R1 is hydrogen or C1-C4-alkyl.
    [0037] 19. The method according to embodiment 18, wherein in addition e) the compounds of the general formula (IV) are subjected to hydrogenation to obtain the compound of the general formula (V)
    where R1 is hydrogen or C1-C4-alkyl.
    [0038] 20. The method according to embodiment 18 or 19, wherein R 1 is hydrogen or methyl, particularly methyl. DESCRIPTION OF THE INVENTION
    [0039] The method according to the invention can be understood in principle as a reactive distillation but in which the reaction zone and the subsequent distillation zone are not necessarily integrally linked to each other. Thus, the catalyst and the cyclopentadecane-1,5-diol used as a reactant remain in the reaction zone (at the bottom), while the residence time of the product in the reaction zone is minimized. This is made possible by the addition of a suitable solvent. In this way, a high conversion of cyclopentadecane-1,5-diol (II) and at the same time improved yield and purity of the product of formula (I) is obtained.
    [0040] The process according to the invention has the following advantages: - the method according to the invention allows a sufficient contact time of the cyclopentadecane-1,5-diol (II) with the catalyst and at the same time a low time contact of the product in the reaction zone.
    [0041] - Distillation separation conditions of compound (I) can then be specifically set to be mild, if the vapor pressure of the solvent used in step b) is between the vapor pressure of compound (I) and the pressure of vapor of compound (II). The vapor pressure of the solvent used in step b) is preferably between the vapor pressure of compound (I) and the vapor pressure of compound (III). Thus, lower temperatures and/or weaker vacuum are required. In the specific embodiment of the invention for the preparation of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) from 3-methylcyclopentadecane-1,5-diol (II.1), the pressure of The vapor of the solvent used in step b) is preferably between the vapor pressure of the compound (I.1) and the vapor pressure of the compound (II.1). The vapor pressure of the solvent used in step b) is therefore particularly preferred between the vapor pressure of the compound (I.1) and the vapor pressure of the compound (III.1)
    [0042] - By using solvents, mixing of the bottom reaction mixture can also be improved
    [0043] - The method according to the invention allows the use of a small amount of catalyst, based on the amount of cyclopentadecane-1,5-diol present in the reaction zone. This advantage is already apparent in a batch mode of operation, without replenishing the converted cyclopentadecane-1,5-diol in the course of the reaction. This advantage is distinctly greater in a mode of operation in which additional cyclopentadecane-1,5-diol is fed into the reaction zone during the course of the reaction. This especially applies to a continuous mode of operation.
    [0044] - The compounds of general formula (I) and especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) can therefore be achieved with high conversion in good yield and purity with the method according to with the invention.
    [0045] In the context of the present invention, R1 is C1-C4-alkyl and is preferably methyl, ethyl, n-propyl, isopropyl or n-butyl.
    [0046] In the compounds of formulas (I), (II), (III), (IV), (V), (VI) and (VII), R 1 is preferably hydrogen or methyl, particularly methyl.
    [0047] In a preferred embodiment, the invention relates to a method for preparing compounds of formula (I.1).

    [0048] The compound of general formula (I.1) is referred to as 14-methyl-16-oxabicyclo[10.3.1]pentadec-12-ene. The specification of the position of the double bond is sometimes omitted below and a synonym for the term 14-methyl-16-oxabicyclo[10.3.1]pentadecene is used.
    [0049] Unless specifically specified in the following, general formulas (I) and (I.1) refer to E/Z mixtures of any composition and pure conformational isomers. Furthermore, general formulas (I) and (I.1) refer to all stereoisomers in pure form and also racemic and optically active mixtures of compounds of formulas (I) and (I.1).
    [0050] Unless specifically specified in the following, general formula (II) refers to mixtures of the possible cis/trans isomers in any composition and also to pure constitutional isomers.
    [0051] The starting material provided in step a) preferably comprises a compound of general formula (II.1):

    [0052] The compound of general formula (II.1) is referred to as 3-methylcyclopentadecane-1,5-diol.
    [0053] In particular, an apparatus is used to carry out the method according to the invention, wherein the apparatus comprises a reaction zone and a distillation zone connected thereto. Specifically, after the start of the reaction in the reaction zone, a portion of the compound of formula (I) is in the distillation zone, even though no compound of formula (I) is (yet) withdrawn therefrom. This can occur, for example, at the beginning of the reaction or during the distillation of the compound of formula (I) in a phased manner, for example, if the content of the compound (I) at the top of the column is very low. Also by means of this procedure, the residence time of the compound of formula (I) in the reaction zone can be minimized and, therefore, its thermal stress.
    [0054] The method according to the invention is particularly suitable for the preparation of 14-methyl-16-oxabicyclo[10.3.1]pentadec-12-ene (I.1), starting from 3-methylcyclopentadecane-1,5-diol (II.1). In this specific embodiment, after the reaction starts in the reaction zone, a portion of the 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) is in the distillation zone, even though no 14-methyl- 16-oxabicyclo[10.3.1]pentadecene (I.1) is withdrawn therefrom.
    [0055] The method according to the invention can be performed continuously, semi-continuously (semi-batch mode) or discontinuously (batch mode).
    [0056] A continuous mode of operation is understood to mean that, in addition to an initial phase at the beginning of the reaction, the compound of general formula (II) (especially 3-methylcyclopentadecane-1,5-diol (II.1)) is continuously fed to the reaction zone and the compound of general formula (I) (especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1)) is continuously distilled off from the reaction mixture. In this case, the compound of general formula (II) is preferably fed depending on the amount of compound of general formula (I) separated. The mixture in the reaction zone is then preferably essentially at steady state, i.e. the concentration of the compound of general formula (II) and the compound of general formula (I) is essentially constant in the reaction mixture.
    [0057] In the batch mode of operation, a portion or the total amount of the compound of general formula (II) is fed to the reaction zone before the start of the reaction. Once a sufficient amount of the compound of general formula (I) has been formed, it is distilled off. Optionally, fresh compound (II) can be introduced into the reaction zone after the content of compound (II) has declined below a certain threshold in the reaction zone. This can be done either once or repeatedly.
    [0058] A semi-continuous mode of operation is also possible, in which one of the steps, adding the compound of general formula (II) or separating the compound of general formula (I), is carried out continuously and the other in batch mode. Step a):
    [0059] The compounds of the general formula (II) and the preparation thereof are known in principle. For example, a compound of the general formula
    where R1 is hydrogen or C1-C4-alkyl, can be subjected to a reaction with hydrogen in the presence of a hydrogenation catalyst.
    [0060] To provide 3-methylcyclopentadecane-1,5-diol (II.1) as a starting material in step a), the 3-methylcyclopentadecane-1,5-dione of formula (III.1)
    it is preferably subjected to a reaction with hydrogen in the presence of a hydrogenation catalyst.
    [0061] Suitable hydrogenation catalysts having a high selectivity for hydrogenation of both keto groups to alcohol groups are, in principle, the transition metal catalysts known to those skilled in the art for hydrogenation reactions. In general, the catalyst comprises at least one transition metal from groups 7, 8, 9, 10 and 11 of the IUPAC Periodic Table. Preferably, the catalyst has at least one transition metal from the group of Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu and Au. The catalyst particularly preferably has Ni. The hydrogenation catalysts consist of the transition metals mentioned as such or comprise the mentioned transition metals applied to a support, as precipitated catalysts, as Raney catalysts or as mixtures thereof.
    [0062] Preference is given to using a Raney catalyst as the hydrogenation catalyst. A suitable hydrogenation catalyst is Raney nickel.
    [0063] The molar ratio of hydrogen to compound (III) is preferably from 1000:1 to 1:1, more preferably from 100:1 to 5:1.
    [0064] The hydrogenation is preferably carried out at a temperature in the range from 10 to 250°C, particularly preferably from 20 to 200°C.
    [0065] The hydrogenation is preferably carried out in the liquid phase in the presence of a solvent.
    [0066] The solvent used for the hydrogenation is preferably selected from water, C1 to C5 aliphatic alcohols, C2 to C6 aliphatic diols, ethers and mixtures thereof. Preferably, the solvent is selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, secbutanol, isobutanol and tert-butanol, ethylene glycol, propane-1,3-diol, butane-1,4-diol , pentane-1,5-diol, hexane-1,6-diol, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, tert-butyl methyl ether and mixtures thereof.
    [0067] The reaction mixture obtained in the hydrogenation of the compound of formula (III), before using it as a starting material in step a) of the method according to the invention, can be subjected to at least one processing step. Suitable processing steps are selected from: - separating the solvent used in the hydrogenation, - separating the non-hydrogenated compound of formula (III), - separating undesirable by-products, or a combination of at least two of the aforementioned measures.
    [0068] Unwanted by-products in the hydrogenation of 3-methylcyclopentadecane-1,5-dione (III) include partially hydrogenated ketoalcohol (3-methylcyclopentadecane-5-ol-1-one) and also unsaturated compounds.
    [0069] The reaction mixture from the hydrogenation of the compound of the general formula (III) is preferably subjected to a distillation separation. In the simplest case, a distillation apparatus for one stage (single) distillation can be used for this distillation. Other suitable apparatus for distillation separation of the reaction mixture from the hydrogenation of compound (III) comprise distillation columns, such as tray columns, which may be equipped with bubble caps, sieve plates, sieve tray, structured packs, valves, side collectors, etc., evaporators such as thin film evaporators, falling film evaporators, forced circulation evaporators, Sambay evaporators, etc., and combinations thereof.
    [0070] Distillation columns can have internal separation parts, preferably selected from separation trays, stacked packs, e.g. sheet metal or fabric packs such as Sulzer Mellapak®, Sulzer BX, Montz B1 or Montz A3 or Kühni Rombopak, or random beds of random packing, such as Dixon rings, Raschig rings, High-Flow rings or Super Raschig rings, for example.
    [0071] In step a) of the method according to the invention, a material is preferably provided with the compound of the general formula II in an amount of at least 50% by weight, particularly preferably at least 70% by weight, particularly at at least 90% by weight, especially at least 95% by weight, based on the total weight of the starting material. This material is then used for the reaction in step (b).
    [0072] In a preferred embodiment in step a) of the method according to the invention, a material is provided with 3-methylcyclopentadecane-1,5-diol (II.1) in an amount of at least 50% by weight , particularly preferably at least 70% by weight, particularly at least 90% by weight, especially at least 95% by weight, based on the total weight of the starting material. This material is then preferably used for the reaction in step (b). Step b):
    [0073] According to the invention, the starting material of step a) comprising the compound of formula (II) is subjected to a reaction in step b) at a temperature in the range of 100 to 240°C and a pressure in the range from 0.1 to 15 kPa (1 to 150 mbar) in the presence of a solvent or a mixture of solvents having a vapor pressure in the range of 1-5 to 10 kPa (10-5 to 100 mbar) at 180°C.
    [0074] At a temperature in the range of 100 to 240°C and a pressure in the range of 0.1 to 15 kPa (1 to 150 mbar), the conversion of 3-methylcyclopentadecane-1,5-diol (II.1) for 14-methyl-16-oxa-bicyclo[10.3.1]pentadecene (I.1) gives the following boiling sequence (low to high boiling): 14-methyl-16-oxabicyclo[10.3.1]pentadecene( I.1), 3-methylcyclopentadecane-1,5-dione (III.1), 3-methylcyclopentadecane-1,5-diol (II.1).
    [0075] The compounds have the following vapor pressures at 180°C: 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1): 2.7 kPa (27 mbar) 3-methylcyclopentadecane-1,5 -dione (III.1): 0.7 kPa (7 mbar) 3-methylcyclopentadecane-1,5-diol (II.1): 0.2 kPa (2 mbar)
    [0076] In principle, any solvent is suitable for use in the method according to the invention which has a vapor pressure under the reaction conditions which is sufficiently below the vapor pressure of the compound of general formula (I), especially 14- methyl-16-oxabicyclo[10.3.[1] ntadecene (I.1). If the solvent forms a low boiling azeotrope with the compound of general formula (I), especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1), the compound (I) or (I. 1) can be separated by distillation together with the solvent or solvent mixture. However, the solvent should preferably not form a high boiling azeotrope with the compound of general formula (I), especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1), whose solvent has a lower vapor pressure than compound (II) or (II.1) at 180°C.
    [0077] The boiling points of most solvents are given in standard works such as the Handbook of Chemistry and Physics, which is published as periodic updates by CRC Press, Inc., in Boca Raton, Florida, USA. In this case, the standard boiling point at 101.325 kPa is usually given. The present boiling point at the temperature and pressure prevailing under the reaction conditions can be determined by applying the Antoine equation or the Claussius-Clapeyron equation. Descriptions of these are found, for example, in Handbook of Chemistry and Physics, 76th Edition (1995-1996), 15-19, CRC Press, Inc., Boca Raton, Florida, USA. The determination of the present boiling point of a specific solvent at the temperature and pressure prevailing under the reaction conditions is also within the ordinary skill of those skilled in the art.
    [0078] In a first variant of the method according to the invention, a solvent is used in step b) with a vapor pressure lower than the vapor pressure of the compound of general formula (II). Specifically, the method according to the invention serves to prepare 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) and a solvent is used in step b) with a vapor pressure which is lower than the vapor pressure 3-methylcyclopenta-decane-1,5-diol vapor (II.1).
    [0079] The vapor pressure refers in this case to the temperature that prevails under the reaction conditions in step b).
    [0080] In a specific configuration of this first variant, the compound of formula (I.1) (14-methyl-16-oxabicyclo[10.3.1]pentadecene) is separated from the reaction mixture by one-stage distillation (i.e., without rectification).
    [0081] In a second preferred variant of the method according to the invention, a solvent is used in step b) with a vapor pressure that is between the vapor pressure of compound (I) and compound (II). Specifically, the method according to the invention serves to prepare 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1), and a solvent is used in step b) having a vapor pressure between the vapor pressure of 14-methyl-16-oxa-bicyclo[10.3.1]pentadecene (I.1) and 3-methylcyclopentadecane-1,5-diol (II.1). In this case, the vapor pressure refers to the temperature prevailing under the reaction conditions in step b). In this variant, it is advantageously possible that during the distillation of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) in step c), 3-methylcyclopentadecane-1,5- unreacted diol (II.1), the catalyst and solvent largely remain in the reaction zone. The product mixture obtained in this case may also comprise 14-methyl-16-oxabicyclo[10.3.1]hexadecane (VI.1) and/or 3-methyl-cyclopentadecane-1,5-dione (III.1), in addition to 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1).

    [0082] If desired, the product mixture which may still contain 14-methyl-16-oxabicyclo-[10.3.1]hexadecane (VI.1) and/or 3-methylcyclopentadecane-1,5-dione (III.1) , in addition to 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1), can be separated by distillation.
    [0083] In a third particularly preferred variant of the method according to the invention, a solvent is used in step b) with a vapor pressure that lies between the vapor pressure of the compound (I) and the vapor pressure of the compound (III). Specifically, the method according to the invention serves to prepare 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1), and a solvent is used in step b) having a vapor pressure between the vapor pressure of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) and 3-methylcyclopenta-decane-1,5-dione (III.1). In this case, the vapor pressure refers to the temperature prevailing under the reaction conditions in step b). In this variant, it is advantageously possible that, during the distillation of 14-methyl-16-oxa-bicyclo[10.3.1]pentadecene (I.1) in step c), 3-methylcyclopentadecane-1,5 -diol (II.1) unreacted, the catalyst and solvent and, if present, 3-methylcyclopentadecane-1,5-dione (III.1), remain largely in the reaction zone.
    [0084] According to the invention, a solvent or a mixture of solvents is used in step b) having a vapor pressure in the range of 1-5 to 10 kPa (10-5 to 100 mbar) at 180°C. The solvent or mixture of solvents preferably has a vapor pressure in the range of 1-4 to 10 kPa (10-4 to 100 mbar), in particular 1-3 to 10 kPa (10-3 to 100 mbar), at 180° Ç.
    [0085] The solvent used in step b) is preferably selected from - aliphatic, cycloaliphatic and aromatic hydrocarbons, - monohydric and polyhydric aliphatic, cycloaliphatic and aromatic alcohols, - ether alcohols, polyether polyols and mono- and dialkyl ethers thereof, aromatic ethers and open-chain aliphatic ethers, - ketones, - esters - mixtures thereof.
    [0086] The solvent used in step b) is particularly preferred of -C10-C30-alkanes, -C6-C30-alkanes, -C2-C30-alkanediols, -polyalkylene glycols and mono- and dialkyl ethers thereof, - mixtures of the same.
    [0087] If the solvent used in step b) comprises at least one C10-C30-alkane or consists of a C10-C30-alkane, this is linear or branched and is preferably selected from C12-C28-alkanes, particularly preferably- C14-C24.
    [0088] Suitable C10-C30-alkanes are, for example, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, n-eicosane, n-heneicosane, n-docosane, n-tricosane, n-tetracosane and the constitutional isomers thereof.
    [0089] Preference is given to use at least one linear C14-C24-alkane as a solvent in step b).
    [0090] In particular, the solvent used in step b) is selected from n-heptadecane, n-octadecane, n-nonadecane, n-eicosane, n-heneicosane and mixtures thereof.
    [0091] If the solvent used in step b) comprises at least one C10-C30-alkanol or consists of a C10-C30-alkanol, the C10-C30-alkyl residues are linear or branched and are preferably selected from alkyl residues -C12-C28, particularly preferably C14-C24-alkyl residues.
    [0092] Suitable C10-C30-alkyl residues are, for example, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n- octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl and the constitutional isomers thereof.
    [0093] It is preferred to use at least one linear C14-C24-alkanol as a solvent in step b).
    [0094] The solvent used in step b) is particularly preferably selected from 1-tetradecanol (myristyl alcohol), 1-pentadecanol, 1-hexadecanol (cetyl alcohol or palmitic alcohol), 1-heptadecanol (margaryl alcohol), 1-octadecanol (stearyl alcohol), isostearyl alcohol, 1-eicosanol (arachidyl alcohol), 1-docosanol (behenyl alcohol), 1-tetracosanol (lignoceryl alcohol) and mixtures thereof.
    [0095] In particular, the solvent used in step b) is selected from 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol and mixtures thereof.
    [0096] Furthermore, the solvent used in step b) preferably comprises at least one polyether polyol or a monoalkyl ether or a dialkyl ether thereof.
    [0097] Suitable polyether polyols and the mono- and di(C1-C6 alkyl ethers) thereof may be linear or branched, preferably linear. Suitable polyetherols and the mono- and di(C1-C6 alkyl ethers) thereof generally have a number average molecular weight in the range of about 200 to 2000, preferably 280 to 1000. Preferred 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 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 comprise the alkylene oxide units copolymerized in random distribution or in the form of blocks. Particularly preferred polyether components are ethylene oxide homopolymers.
    [0098] Suitable polyether components PE) are additionally the mono- and di(C1-C2-alkyl ethers) of the above-described polyetherols. Preference is given to polyalkylene glycol monomethyl ethers and polyalkylene glycol dimethyl ethers.
    [0099] Suitable polyalkylene glycols are polyethylene glycols obtainable from BASF SE under the brand name Lutrol E®. Particularly suitable is Lutrol E® 400 with an average of 8 repeating units of ethylene oxide.
    [00100] The solvent content of the reaction mixture in step b) is preferably always maintained at at least 20% by weight, preferably at least 30% by weight, in particular at least 50% by weight, based on the total weight of the reaction mixture into the reaction zone.
    [00101] The amount of catalyst in the reaction zone is preferably from 0.001 to 5% by weight, particularly preferably from 0.01 to 3% by weight, based on the total weight of the reaction mixture in the reaction zone.
    [00102] The amount of catalyst in the reaction zone is preferably from 0.1 to 15% by weight, particularly preferably from 0.5 to 10% by weight, particularly from 1 to 5% by weight, based on weight maximum of the compound of general formula (II), especially 3-methylcyclopentadecane-1,5-diol (II.1) present in the reaction zone.
    [00103] The above mentioned values for the amount of catalyst in the reaction zone apply, in principle, to batch, semi-continuous and continuous modes of operation. The catalysts used according to the invention are characterized by a good service life such that fresh cyclopentadecane-1,5-diol(II) can be introduced into the reaction zone for a long reaction time without the catalyst activity being affected. decrease sharply. The method according to the invention thus allows the preparation of compounds of general formula (I) from cyclopentadecane-1,5-diols (II) using very low amounts of catalyst based on total conversion.
    [00104] Reactors that can be used as a reaction zone in step b) are not subject to any particular limitations. Therefore, at least one stirred reactor, at least one tubular reactor or at least one closed loop reactor, for example, can be used as reactors. Reactors can be equipped with at least one internal and/or at least one external heat exchanger. It is also possible to configure at least one of these reactors so that it has at least two different zones. Such zones may, for example, differ in reaction conditions such as, for example, temperature or pressure, and/or in zone geometry such as, for example, volume or cross-section. If the reaction is carried out in two or more reactors, two or more identical types of reactors or at least two different types of reactors can be used.
    [00105] The cyclopentadecane-1,5-diol (II) is advantageously introduced into the reaction zone in liquid form. In a first preferred embodiment, a melt of cyclopentadecane-1,5-diol(II) is introduced into the reaction zone. In a second preferred embodiment, the cyclopentadecane-1,5-diol (II) is introduced into the reaction zone as a solution in the used solvent. If the method according to the invention is carried out in batch mode, the cyclopentadecane-1,5-diol (II) is preferably initially partially or completely loaded into the reaction zone.
    [00106] As discussed, the method according to the invention is specifically for the preparation of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) from 3-methylcyclopentadecane-1,5-diol ( II.1). If 3-methylcyclopentadecane-1,5-diol (II.1) is fed into the reaction zone during the course of the reaction in step b), in a first preferred embodiment, a melt of 3-methylcyclopentadecane-1,5 -diol (II.1) is introduced into the reaction zone. This variant is suitable for batch, semi-continuous or continuous operating modes. Since in this variant the high-boiling solvent used according to the invention is not fed additionally to the reaction zone, the accumulation of the same can be effectively avoided.
    [00107] In a second preferred embodiment, the 3-methylcyclopentadecane-1,5-diol (II.1) is fed to the reaction zone as a solution in a low boiling solvent during the course of the reaction in step B). For this purpose, the same low boiling solvents can be used as for feeding the suspension catalyst into the reaction zone. These low boiling solvents can be removed by distillation in the first stage at the beginning of the reaction. Furthermore, these low boiling solvents can be condensed at the top of the column together with the 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) and discharged. Alternatively, low boiling solvents can also be discharged in gaseous form.
    [00108] In a third embodiment, 3-methylcyclopentadecane-1,5-diol (II.1) is fed to the reaction zone as a solution in the solvent (high boiling point) used according to the invention during the course of the reaction in step b). This variant is not preferred for the continuous feeding of 3-methylcyclopentadecane-1,5-diol (II.1), as it can lead to an accumulation of the solvent in the reaction zone. A distillation separation of this high boiling solvent, together with 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1), is possible in a one-stage distillation.
    [00109] A heterogeneous catalyst that is capable of dehydrogenating and dehydrating cyclopentadecane-1,5-diol(II) is used for the reaction in step b).
    [00110] The catalysts used in step b) preferably comprise at least one transition metal from groups 7, 8, 9, 10 and 11 of the IUPAC Periodic Table. The catalysts used in step b) more preferably comprise at least one element selected from the group consisting of Cu, Co, Rh, Ir, Ni, Pd, Re, Fe, Ru and Au. The catalysts used particularly preferably comprise Cu. In a specific embodiment, copper is the only metal used in the active mass of the catalyst.
    [00111] The catalysts used in step b) comprise said transition metals, especially the transition metals mentioned as preferred, generally as such, applied to a support, as precipitation catalysts, as Raney catalysts or as mixtures thereof. Raney copper is especially used in step b).
    [00112] The inert support materials used for the catalysts used in step b) can be practically all prior art support materials used advantageously in the preparation of supported catalysts, for example carbon, SiO2 (quartz), porcelain, magnesium oxide , tin dioxide, silicon carbide, TiO2 (rutile, anatase), Al2O3 (alumina), aluminum silicate, steatite (magnesium silicate), zirconium silicate, cerium silicate or mixtures of these support materials. Preferred support materials are carbon, aluminum oxide and silicon dioxide.
    [00113] If two or more metals are used, they may be present separately or as an alloy. It is possible in this case to use at least one metal as such and at least one other metal as Raney catalyst or at least one metal as such and at least one other metal applied to at least one support, or at least one metal as Raney catalyst and at least one other metal applied to the at least one support, or at least one metal as such and at least one other metal as a Raney catalyst and at least one other metal applied to the at least one support.
    [00114] Catalysts can be used in the form of shaped bodies, for example in the form of spheres, rings, cylinders, cubes, cuboids or other geometric bodies. Unsupported catalysts can be formed by customary processes, for example by extrusion, tablets, etc. The shape of supported catalysts is determined by the shape of the support. Alternatively, the support may be subjected to a shaping process before or after application of the catalytically active component(s). Catalysts can be used, for example, in the form of pressed cylinders, pellets, pellets, wagon wheels, rings, stars or extrudates such as solid extrudates, polylobal extrudates, hollow extrudates and honeycombs, or other geometric bodies.
    [00115] Suitable reactors for the reaction in step b) are reactors known to those skilled in the art that are suitable for reactions under simultaneous evaporation of a component and/or release of a gaseous component and/or reaction under reduced pressure. These include, for example, stirred tanks (which can also be configured as stirred tank cascades), tube reactors, tube bundle reactors, circulation reactors, etc.
    [00116] To provide the necessary heat for the reaction in step b) and the distillation separation of compound (I), especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1), in step c) , one or more of the reactors may be provided with at least one heating device. If a single reactor is used, this is usually provided with a heating device. If two or more reactors are used, usually at least the first reactor, especially all reactors, is/are provided with a heating device. Heat can also be provided at least in part by heating an external circulating stream or by internal heating in at least one of the reactors. For internal heating, it is possible to use the usual devices for this purpose, generally hollow modules, such as field tubes, tube coils, heat exchanger plates, etc. Alternatively, the reaction can also be carried out in a heated tube bundle reactor.
    [00117] Step b) of the method according to the invention, using at least one heterogeneous catalyst, can be carried out in fixed bed mode or in suspension mode. Operation in the fixed bed mode can be conducted here, for example, in the liquid phase mode or in the drip mode.
    [00118] If, for example, step b) is carried out with at least one catalyst in suspension, the reaction zone preferably comprises at least one stirred reactor. Heterogeneous catalysts are generally used here in a finely divided state and are in fine suspension in the reaction medium. For this purpose, the catalyst is preferably introduced into the reaction zone as a suspension in the solvent used according to the invention or a low boiling solvent different therefrom. Suitable low boiling solvents other than the solvents used according to the invention are preferably selected from water, C1 to -C4 alkanols and mixtures thereof. Preference is given to water, methanol and mixtures thereof. These low boiling solvents can be removed by distillation before or at the beginning of the reaction. Generally, the procedure in such cases is to initially load the slurry catalyst into the reaction zone. This procedure is independent of whether the method according to the invention is carried out in batch, semi-continuously or continuously. The catalysts used are characterized by a long service life. It is possible, however, in the case of declining catalyst activity, especially in the continuous process, to introduce a fresh catalyst slurry into the reaction zone. In this case, the newly introduced suspension catalyst is preferably used as a suspension in the solvent used according to the invention. Step c):
    [00119] In step c) of the method according to the invention, a fraction comprising the compound of formula (I) is distilled off from the reaction mixture present in the reaction zone.
    [00120] Specifically, the method according to the invention serves to prepare 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) from 3-methylcyclopentadecane-1,5-diol (II.1) . Then, in step c) of the method according to the invention, a fraction comprising the compound of formula (I.1) (14-methyl-16-oxabicyclo[10.3.1]pentadecene) is distilled off from the mixture of reaction present in the reaction zone.
    [00121] In particular, an apparatus is used to carry out the method according to the invention, wherein the apparatus comprises a reaction zone and a distillation zone connected thereto. In a preferred embodiment, the apparatus according to the invention used to carry out steps b) and c) comprises a stirred tank or a stirred tank cascade, wherein the stirred tank, or in the case of a stirred tank cascade, is the final stirred tank is provided with a distillation apparatus in the flow direction.
    [00122] The reaction in step b) and also the distillation separation of a fraction comprising the compound of formula (I) (especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1)) in step c ) is preferably carried out at a temperature in the range of 100 to 240°C. The temperature is particularly preferred in the range of 120 to 220°C.
    [00123] The reaction in step b) and also the distillation separation of a fraction comprising the compound of formula (I) (especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1)) in step c ) is preferably carried out at a pressure in the range of 0.01 to 10 kPa (0.1 to 100 mbar). Pressure is particularly preferred in a range of 0.05 to 5 kPa (0.5 to 50 mbar).
    [00124] The first filling of the reaction zone is preferably carried out before the start of the reaction at a temperature in the range of 10 to 100°C, preferably 15 to 70°C. The temperature is determined here by the components of the reaction mixture used. If, for example, hexadecanol is used as a solvent, the filling is advantageously carried out above the melting temperature of 49°C. If, for example, methanol is used as a co-solvent to charge the catalyst suspension, the filling is advantageously carried out below the boiling temperature of about 67°C. The temperature during the reaction in step b) and the distillation separation in step c) may also be increased in one or more steps or continuously, for example, to accelerate the separation of the compound of general formula (I) formed during the reaction. Furthermore, the temperature during the reaction in step b) and the distillation separation in step c) can also be reduced in one or more steps or continuously, for example to feed components to the reaction zone, such as cyclopentadecane-1 fresh ,5-diol (II), fresh solvent or fresh catalyst and/or in order to stop the separation of the compound of general formula (I), for example, in order to increase again the content of the compound of general formula (I) in the reaction zone after a separation step.
    [00125] The first filling of the reaction zone preferably takes place at atmospheric pressure before the start of the reaction. The pressure during the reaction in step b) and the distillation separation in step c) can also be reduced in one or more steps or continuously, for example, in order to accelerate the separation of the compound of general formula (I) formed during the reaction. reaction. Furthermore, the pressure during the reaction in step b) and the distillation separation in step c) can also be increased in one or more steps or continuously, for example, in order to feed components into the reaction zone, such as cyclopentadecane -1,5-diol (II) fresh, fresh solvent or fresh catalyst and/or in order to stop the separation of the compound of the general formula (I), for example, in order to increase again the content of the compound of the general formula ( I) in the reaction zone after a separation step.
    [00126] Optionally, before the start of the present reaction, the pressure in the reaction zone and in the distillation zone is initially reduced (optional stage 1). Furthermore, before the start of the present reaction, the temperature in the reaction zone can already be raised. This stage 1, however, is characterized in that the temperature is below 100°C and/or the pressure is above 10 kPa (100 mbar). In a preferred embodiment, the pressure is initially reduced in the stage before the start of the reaction, preferably to a value in the range of 10 to 50 kPa (100 to 500 mbar), particularly preferably 18 to 30 kPa (180 to 300 mbar). amber). At this stage, the temperature is preferably not increased or increased to a maximum of 50°C compared to the temperature at the first filling of the reaction zone. In a specific embodiment, the reaction in step b) is carried out with at least one suspension catalyst, wherein the catalyst is introduced into the reaction zone in a low-boiling solvent. These low boiling solvents are preferably removed by distillation in the first stage at the beginning of the reaction.
    [00127] After stage 1, the pressure in the reaction zone and in the distillation zone is preferably reduced in stages or continuously. Simultaneously or independently, the temperature can be increased stepwise or continuously.
    [00128] Optionally, the reaction in step b) comprises a phase during which the temperature in the reaction zone is in the range of 100 to 240°C and the pressure in the reaction zone and in the distillation zone is in the range of 0, 01 to 15 kPa (0.1 to 150 mbar), but wherein none of the fraction comprising the compound of formula (I) is distilled off from the reaction mixture (optional step 2). At this stage, the compound of general formula (I) (especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1)) is formed in the reaction zone from the compound of general formula (II) (especially 3-methylcyclopentadecane-1,5-diol (II.1)) such that the concentration of the compound of general formula (I) (especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1)) increases in the reaction mixture. Specifically, a portion of the compound of general formula (I) (especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1)) is in the distillation zone in stage 2, even though no compound of general formula ( I) (especially 14-methyl-16-oxa-bicyclo[10.3.1]pentadecene (I.1)) is taken therefrom. By means of this procedure, the residence time of the compound of general formula (I) (especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1)) in the reaction zone can be minimized and therefore its thermal phase.
    [00129] The reaction in step b) comprises a phase during which the temperature in the reaction zone is in the range of 100 to 240°C and the pressure in the reaction zone and in the distillation zone is in the range of 0.01 to 15 kPa (0.1 to 150 mbar), and wherein the compound of formula (I) (especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1)) is distilled off from the reaction mixture (phase 3).
    [00130] In the simplest case of carrying out the method according to the invention in batch mode without replenishing the cyclopentadecane-1,5-diol (II), step 3 is carried out once until the cyclopentadecane-1,5-diol (II) in the reaction zone is converted as far as possible to compound (I) and this is separated as far as possible from the reaction mixture by distillation.
    [00131] In the ideal case of continuously carrying out the method according to the invention, step 3 is carried out until, despite feeding cyclopentadecane-1,5-diol (II) and optionally other components (such as solvent or catalyst) into the reaction zone, the concentration of compound (I) in the reaction zone has decreased to such an extent that an effective separation by distillation, i.e. in sufficient quantity and purity, is no longer possible in a technically feasible manner.
    [00132] Optionally, the reaction in step b) comprises a step (optional step 4) in which the distillation separation of compound (I) from the reaction mixture is stopped. Such a phase can serve the purpose, for example, of feeding components to the reaction zone, such as fresh cyclopentadecane-1,5-diol (II), fresh solvent or fresh catalyst and/or to increase the content of compound (I) again. in the reaction zone after a separation step.
    [00133] Another phase 3 can follow from phase 4, in which phases 3 and 4 can, in principle, be carried out successively as many times as desired.
    [00134] In the simplest case, the distillation zone (ie the distillation apparatus used in accordance with the invention) consists of an apparatus for one-stage (simple) distillation. The person skilled in the art is aware of suitable apparatus for one-stage distillation. In such an apparatus, essentially no exchange of substance between vapors and condensate takes place. In other words, simple distillation takes place without rectification. In this embodiment, a solvent is preferably used in step b) with a vapor pressure lower than the vapor pressure of cyclopentadecane-1,5-diol (II). In this case, the vapor pressure refers to the temperature prevailing under the reaction conditions in step b). The solvent is then preferably selected from polyalkylene glycols and mono and dialkyl ethers thereof. In particular, through the addition of the solvent, better mixing of the reaction zone is ensured. Alternatively, a solvent is used with a vapor pressure that is between the vapor pressure of compound (I) and the vapor pressure of compound (II). Specifically, the method according to the invention serves to prepare 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) from 3-methylcyclopentadecane-1,5-diol (II.1). Preference is therefore given to using a solvent with a vapor pressure that is between the vapor pressure of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) and the vapor pressure of 3-methylcyclopentadecane-1 ,5-diol. The temperature can thus be kept low. Furthermore, the content of compound (I) in the reaction zone can thus be more easily kept at a low level. The solvent can then be subsequently separated from compound (I), for example by distillation.
    [00135] The product separated by one-stage distillation in step c) preferably has a content of the compound of general formula (I) of 75 to 95% by weight, based on the total weight of the separated product.
    [00136] Specifically, the method according to the invention serves to prepare 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) from 3-methylcyclopentadecane-1,5-diol (II.1) . The product separated by one-stage distillation in step c) then preferably has a 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) content of 75 to 95% by weight, based on the total weight of the separate product.
    [00137] In a typical composition for the preparation of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) from 3-methylcyclopentadecane-1,5-diol (II.1), the product is separated by one-stage distillation in step c) comprises the following compounds, each based on the total weight of the separated product: 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1): 75 - 95% by weight , 3-methylcyclopentadecane-1,5-diol (II.1): 0 - 5% by weight, 3-methylcyclopentadecane-1,5-dione (III.1): 1 - 10% by weight, 14-methyl-16 -oxabicyclo[10.3.1]hexadecane (VI.1): 0-15% by weight.
    [00138] The product separated by one-stage distillation in step c) can, if desired, be subjected to further processing. The product separated by one-stage distillation in step c) is preferably subjected to further distillation to obtain at least one fraction enriched in compound (I) (especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1)) and at least a fraction depleted in compound (I) (especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1)). Suitable distillation apparatus are those mentioned in step a) for distilling off the reaction mixture from the hydrogenation of compound (III).
    [00139] For the distillation separation of compound (I) (especially 14-methyl-16-oxabicyclo-[10.3.1]pentadecene (I.1)) obtained in the reaction in step b), all apparatus for the separation by distillation of reaction mixtures comprising liquid components are generally suitable. Suitable apparatus include distillation columns, such as tray columns, which can be equipped with bubble caps, sieve plates, sieve tray, structured packs, random packs, valves, side collectors, etc., evaporators such as film evaporators. thin, falling film evaporators, forced circulation evaporators, Sambay evaporators, etc., and combinations thereof. Suitable structured packaging or random packaging are, for example, sheet metal or fabric packaging such as Sulzer Mellapak®, Sulzer BX, Montz B1 or Montz A3 or Kühni Rombopak, or random beds of random packaging such as Dixon rings, Raschig rings, High-Flow rings or Super Raschig rings, for example.
    [00140] For the distillation separation of compound (I) (especially 14-methyl-16-oxabicyclo-[10.3.1]pentadecene (I.1)) obtained in the reaction in step b), at least one distillation column of a particularly preferred mode is used. In particular, at least one distillation column having at least 10 theoretical plates is used for the distillation separation of compound (I) (especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1)) obtained in reaction in step b). The distillation column used for distillation separation usually in direct connection with the reaction zone, eg a stirred reactor. For the reaction in step b) and for the distillation separation of compound (I) (especially 14-methyl-16-oxabicyclo-[10.3.1]pentadecene (I.1)) in step c), a stirred reactor is preferably used for which a distillation column has been installed. The stirred reactor thus functions primarily as a heated bottom for the distillation column. In the case of using two or more reactors connected in series, each of these reactors can be equipped with a distillation column or the vapor-containing compound (I) can be fed through one or more lines to a distillation column, preferably from the last tank of the reactor cascade in the flow direction.
    [00141] For the distillation separation of compound (I) (especially 14-methyl-16-oxabicyclo-[10.3.1]pentadecene (I.1)) obtained in the reaction in step b) using at least one distillation column, the solvent used according to the invention preferably has a vapor pressure between the vapor pressure of compound (I) and the vapor pressure of compound (II). The solvent used according to the invention particularly preferably has a vapor pressure which is between the vapor pressure of compound (I) and the vapor pressure of compound (III). Suitable and preferred solvents mentioned above for use in step b) are fully incorporated by reference.
    [00142] Compound (I) (especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1)) released in the reaction in step b) is preferably separated from the reaction mixture in a batch or continuously .
    [00143] In a specific embodiment, a compound (II) (especially 3-methylcyclopentadecane-1,5-diol (II.1)) is continuously fed to the reaction zone and the compound (I) (especially 14-methyl - 16-oxabicyclo[10.3.1]pentadecene (I.1)) released is continuously separated from the reaction mixture.
    [00144] The product separated by fractional distillation in step c) preferably has a content of compound (I) (especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1)) of 80 to 99% by weight , particularly preferably 85 to 99% by weight, based on the total weight of the separated product.
    [00145] In a typical composition for the preparation of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) from 3-methylcyclopentadecane-1,5-diol (II.1), the separated product by fractional distillation in step c) comprises the following compounds, each based on the total weight of the separated product: - 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1): 80 - 99% by weight, - 3-methylcyclopentadecane-1,5-diol (II.1): 0 - 5% by weight, - 3-methylcyclopentadecane-1,5-dione (III.1): 0 to 5% by weight, preferably 0 to 1% by weight, - 14-methyl-16-oxabicyclo[10.3.1]hexadecane (VI.1): 0 to 15% by weight, preferably 0 to 10% by weight, - solvent: 0 to 5 % by weight, preferably 0 to 1% by weight, - 3-methylcyclopentadecan-5-ol-1-one (VII.1): 0-5% by weight.
    [00146] Other compositions of the reaction mixture can also be obtained depending on the selected reaction conditions.
    [00147] In the distillation separation in step c) of the compound (I) (especially 14-methyl-16-oxa-bicyclo[10.3.1]pentadecene (I.1)) obtained in the reaction in step b), a vapor initially removed, which is subsequently at least partially condensed. Condensation or partial condensation of the steam may be carried out using any suitable condensers. These can be cooled with any desired cooling medium. Preference is given to air-cooled and/or water-cooled condensers. The condenser is generally located at the top, i.e. at the upper end of the distillation column or is integrated into the head of the column.
    [00148] In the context of the present invention, the terms "top of column" or "head of column" are understood to mean the region of a distillation column that is located at the upper end, that is, generally in the upper fifth, preferably in the tenth top of the distillation column.
    [00149] Generally, the ratio of flux removed to flux recirculated in the column is in the range of 1:1 to 1:30, and especially in the range of 1:1 to 1:20.
    [00150] Typically, the separation of compound (I) (especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1)) obtained in the reaction in step b) is started as soon as the temperature at the head of the column no longer changes essentially after the start of the reaction in step b). This is the case, for example, after a few minutes to a few hours.
    [00151] During the distillation separation of compound (I) (especially 14-methyl-16-oxabicyclo-[10.3.1]pentadecene (I.1)) obtained in the reaction in step b), the reflux ratio as defined above, is preferably adjusted so that the temperature at the head of the column remains constant as much as possible. The expression "constant as much as possible" in this context means that the temperature at the head of the column fluctuates by less than 10°C, for example less than 5°C or 3°C. In other words, the reflux ratio at the head of the column is adjusted so that the composition (purity) of the overhead stream relative to compound (I) (especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I) .1)) remains essentially constant.
    [00152] In a preferred embodiment of the method according to the invention, at least one compound (II) (especially 3-methylcyclopentadecane-1,5-diol (II.1)) is additionally fed to the reaction in step b) . The at least one compound (II) for the reaction in step b) may be fed in stages or continuously, preferably continuously throughout the entire course of the reaction. By means of feeding, the loss of compound (II) in the reaction mixture caused by the distillation discharge of compound (I) (especially 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1)) must be compensated for . At least one compound (II) is preferably fed such that the amount of compound (II) in the reaction mixture during the distillation discharge of compound (I) (especially 14-methyl-16-oxabicyclo[10.3.1] pentadecene (I.1)) remains constant as much as possible. Step d):
    [00153] In a specific embodiment of the method according to the invention, compounds of the general formula (I) are subjected to an additional reaction to obtain at least one compound of the general formula (IV).
    where the symbol
    is in one case a single bond and in one case a double bond and R1 is hydrogen or C1-C4-alkyl.
    [00154] In a specific embodiment, R1 is methyl. Step d):
    [00155] In another specific embodiment of the method according to the invention, the compounds of the general formula (IV) are subjected to an additional reaction to obtain at least one compound of the general formula (V).
    where R1 is hydrogen or C1-C4-alkyl.
    [00156] In a specific embodiment, R1 is methyl. DESCRIPTION OF THE FIGURES
    [00157] Figure 1 shows an apparatus which is, in principle, suitable for the continuous, semi-continuous (semi-batch) or discontinuous (batch) modes of carrying out the method according to the invention. 3-Methylcyclopentadecane-1,5-diol is introduced into the R reactor and reacts in the presence of a heterogeneous catalyst. In the batch mode of operation, 3-methylcyclopentadecane-1,5-diol is added before the reaction starts. Optionally, after the decline of the 3-methylcyclopentadecane-1,5-diol content in the R reactor below a certain threshold, fresh 3-methylcyclopentadecane-1,5-diol can be introduced into the R reactor. as repeatedly. In continuous mode of operation, 3-methylcyclopentadecane-1,5-diol is added depending on its consumption for the preparation of 14-methyl-16-oxabicyclo[10.3.1]pentadecene. The 14-methyl-16-oxabicyclo[10.3.1]pentadecene formed in reactor R is separated by distillation via column K and is condensed in a condenser connected to heat exchanger W. A semi-continuous mode of operation is also possible, in which a of the steps, the addition of 3-methylcyclopentadecane-1,5-diol or the separation of 14-methyl-16-oxa-bicyclo-[10.3.1]pentadecene, is carried out continuously and the other in batch mode.
    [00158] The following examples serve to illustrate the invention, but without restricting it in any way. EXAMPLES
    [00159] List of compounds: - 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1), - 3-methylcyclopentadecane-1,5-diol (II.1), - 3-methylcyclopentadecane-1, 5-dione (III.1), - 14-methyl-16-oxabicyclo[10.3.1]hexadecane (VI.1), - 3-methylcyclopentadecan-5-ol-1-one (VII.1).
    [00160] Gas chromatographic analyzes were performed according to the following method: GC system: Agilent 7890 Series A - column: DB WAX 30 m (length) x 0.32 mm (internal diameter); FD 0.25 μm (film); injector temperature: 230°C; detector temperature 280°C; flow rate: 1.5 ml temperature program: Initial temperature: 80°C to 250°C at 3°C/min, 250°C, 15 minutes isothermal.
    [00161] The compounds present in the measured samples may have different isomers, for example, in relation to the position of the substituents in the ring system (cis, trans isomers) and the position of the substituents in the double bonds. As these isomers have different retention times, the sum total of all determinable area integrals was generated to determine the amount of the compound in question. Retention times are specified below. Example 1: (comparative, reaction without addition of solvent)
    [00162] 4.0 g of catalyst suspension (Raney copper, 30% in water) was initially charged into a 100 ml three-neck flask with 15.08 g of 3-methylcyclopentadecane-1,5-diol (II .1) (84.7% area by GC). The pressure was initially reduced to 22 kPa (220 mbar) at room temperature. The reaction mixture was then heated from room temperature to 166°C and at the same time the pressure was reduced from 22 kPa (220 mbar) to 4 kPa (40 mbar), after which most of the water in the catalyst suspension and also from methanol was distilled. After increasing the temperature to 172 to 176°C and reducing the pressure to 0.1 to 0.2 kPa (1 to 2 mbar), the mixture was stirred for a further 5 h. The temperature was then increased to 180°C and the distillate was removed in one stage (without rectification) over 12 h. The head temperature was 165°C at the beginning of distillate collection and increased in the course of distillation to 175°C. In total, 10 g of distillate were obtained. The content of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) in the distillate was 10.6%, that of 3-methylcyclopentadiene-1,5-dione (III.1) was 27.7% and that of 3-methylcyclopentadecane-1,5-diol (II.1) was 8.3%. This corresponds to a yield of 9%. Example 2: (inventive)
    [00163] 3 g of catalyst suspension (Raney copper, 50% in water) was washed three times with methanol. 10 g of 3-methylcyclopentadecane-1,5-diol (II.1) (82.5% by weight by GC) in 20 g of polyethylene glycol (about 8 PEG units, Lutrol® E400 from BASF SE, pressure of steam at 180°C: 0.02 mbar) were then initially charged at room temperature into a 100 ml three-neck flask together with the washed catalyst. The methanol and residual water were slowly distilled at 50°C at a pressure of 25 to 0.3 kPa (250 to 3 mbar). The reaction mixture was then heated to 200 °C at a pressure of 2 kPa (20 mbar). The temperature was maintained for 16 hours. The pressure was then lowered to 1 mbar and the low boiling components distilled in one stage. Good mixing was ensured throughout the experiment by means of a magnetic stirrer. 4.5 g of distillate with a 14-methyl-16-oxabicyclo[10.3.1]pentadecene content of 87.2% area by GC can be obtained, which corresponds to a yield of 52%. The 3-methylcyclopentadecane-1,5-diol content was 0.8 area% by GC and the 3-methylcyclopentadecane-1,5-dione content was 3.9 area% by GC. Example 3: (inventive, reaction mixture diluted with high boiling solvent, boiling between 14-methyl-16-oxabicyclo[10.3.1]pentadecene and 3-methylcyclopentadecane-1,5-dione)
    [00164] 0.25 g of catalyst suspension (active Raney copper, 50% in water) was washed three times with methanol. 5 g of 3-methylcyclopentadecane-1,5-diol (II.1) (82.7% area by GC) in 10 g of 1-hexadecanol (vapor pressure at 180°C: 1.1 kPa (11 mbar )) were then initially loaded at room temperature into a 100 ml three-neck flask together with the washed catalyst. Good mixing was ensured throughout the experiment by means of a magnetic stirrer. The temperature was initially raised to 70°C to melt the 1-hexadecanol. Methanol and residual water were slowly distilled at 70°C. The reaction mixture was then heated to 180°C at a pressure of 40 mbar with constant stirring. The temperature was maintained for 20 hours. A sample was collected every 1, 3, 5 and 20 h and analyzed by GC. In Table 1 below, the contents of the 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) product of the 3-methylcyclopenta-decane-1,5-diol (II.1) used and also of the compounds ( III.1), (VI.1) and (VII.1) are given as % area per GC (area GC) (without considering 1-hexadecanol) as a function of reaction time. Table 1

    [00165] The pressure was then reduced to 0.1 kPa (1 mbar) and the bottom temperature to 124 to 140°C (see Table) and the low boiling components could be distilled in one stage. Three distilled fractions could be withdrawn (Fr1: 0.6 g, Fr2: 1.3 g, Fr3: 7.3 g). All three fractions were solid and white. Table 2

    [00166] Example 3 was repeated using nonadecane (vapour pressure at 180°C: 11 mbar), tetradecanol (vapour pressure at 180°C: 3.4 kPa (34 mbar)), heptadecanol (vapour pressure at 180 °C: 0.7 kPa (7 mbar)) and octadecanol (vapor pressure at 180 °C: 0.4 kPa (4 mbar)) as solvent. In each case, product fractions with high 14-methyl-16-oxabicyclo[10.3.1]pentadecene content could be isolated. Example 4: (inventive, reaction mixture diluted with hexadecanol, which boils between 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) and 3-methylcyclopentadecane-1,5-dione (III.1), 14-methyl -16-oxabicyclo[10.3.1]pentadecene was removed by stage distillation together with hexadecanol, 3-methylcyclopentadecane-1,5-diol (II.1) was replaced by hexadecanol)
    [00167] 0.5 g of catalyst suspension (active Raney copper, 50% in water) was washed three times with methanol. 10 g of 3-methylcyclopentadecane-1,5-diol (II.1) (85.1% area by GC) in 20 g of 1-hexadecanol (vapor pressure at 180°C: 1.1 kPa (11 mbar )) were then initially loaded at room temperature into a 100 ml three-neck flask together with the washed catalyst. The temperature was initially raised to 70°C to melt the 1-hexadecanol. Methanol and residual water were slowly distilled at 70°C. The reaction mixture was then heated to 180°C at a pressure of 4 kPa (40 mbar). The temperature was maintained for 2 h. The temperature was then lowered to 145°C and the pressure to 0.3 kPa (3 mbar) and 7 g (Fraction 1) was distilled in one stage. The distillate was analyzed and, based on the removed 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1), 3-methylcyclopentadecane-1,5-diol (II.1) together with 1-hexadecanol, was fed to the reactor so that a ratio of 3-methylcyclopentadecane-1,5-diol/1-hexadecanol resulted as in the starting reaction mixture. The temperature was then increased again to 180°C and the pressure to 4 kPa (40 mbar) and held for 2 h. The pressure and temperature were then lowered back to the above-mentioned values and 4.5 g (fraction 2) and 4.8 g (fraction 3) were distilled. 3- Methylcyclopentadecane-1,5-diol (II.1) and 1-hexa-decanol were fed back to the reactor. Using the same procedure described above, a fourth fraction (fraction 4) of 10.8 g was generated. After distillation of fraction 4, without additional addition of 3-methylcyclopentadecane-1,5-diol and 1-hexadecanol, the reaction mixture was kept at 180°C and 4 kPa (40 mbar) for another 24 h and finally 5.1 g of distillate (fraction 5) were distilled. Table 3

    a) reagent (t = 0) b) funds before removing fraction 1 c) fraction 1 b) funds after removing fraction 1 e) funds after adding 3-methylcyclopentadecane-1,5-dione (II.1) )/1- hexadecanol f) fraction 2 g) fraction 3 h) funds after removal of fraction 3 i) funds after the addition of 3-methylcyclopentadecanol-1,5-dione (II.1)/1- hexadecanol k) fraction 4 l) funds after withdrawal of fraction 4 m) fraction 5 n) funds after withdrawal of fraction 5 Example 5: (inventive, solvent-diluted reaction mixture boiling between 14-methyl-16-oxabicyclo[10.3.1]pentadecene (II.1) and 3-methylcyclopentadecane-1,5-dione (III.1) and also removed from 14- methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) via a column)
    [00168] 1.5 g of catalyst suspension (active Raney copper, 50% in water) was washed three times with methanol. 30 g of 3-methylcyclopentadecane-1,5-diol (II.1) (95.2% area by GC) in 60 g of 1-hexadecanol (vapor pressure at 180°C: 1.1 kPa (11 mbar )) were then initially loaded at room temperature into a 100 ml three-neck flask together with the washed catalyst. A structured packing column was placed in the flask (structured packing bed height 53 cm, structured packing 3 mm, Raschig rings, column inner diameter: 1.5 cm). The temperature was initially raised to 70°C to melt the 1-hexadecanol. Methanol and residual water were slowly distilled at 70°C. The reaction mixture was then heated to 181°C at 0.3 kPa (3 mbar) top pressure with mixing by a magnetic stirrer. After 1 h, a distillate flow is established, in which distillate was initially collected at the top of the column under total reflux at a top pressure of 0.2 to 0.3 kPa (2 to 3 mbar). Over the next 2.5 h, a total of 10.6 g of distillate (fraction 1, Fr1) was withdrawn. Under constant conditions, each of the fractions was collected after a further 3 h and 6 h (fraction 2, Fr2: 10.0 g, fraction 3, Fr3: 3.9 g). The hexadecanol content of all fractions was less than 0.5%. The content of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) was 92% in fraction 1, 87% in fraction 2 and 57.8% in fraction 3. In total, this corresponds to an 80% yield.
    [00169] 3-Methylcyclopentadecane-1,5-dione could not be detected in any of the fractions. The main by-product in the distillate was ether. Table 4
    Example 6: (inventive, solvent-diluted reaction mixture boiling between 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) and 3-methylcyclopentadecane-1,5-dione (III.1), continuous reaction procedure with feed and also continuous withdrawal of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) via a column)
    [00170] 2.25 g of catalyst (active Raney copper, distributed in water, taken from the fixed bed) was washed three times with methanol. 90 g of 3-methylcyclopentadecane-1,5-diol (II.1) (97.1% by weight by GC) in 180 g of 1-hexadecanol (vapor pressure at 180°C: 1.1 kPa (11 mbar )) were then initially loaded at room temperature into a 500 ml three-neck flask together with the washed catalyst. A column with structured packing was placed in the flask (pack height 60 cm, Montz structured packing DN30 A3-1000). The temperature was initially raised to 70°C to melt the 1-hexadecanol. Methanol and residual water were slowly distilled at 70°C. The reaction mixture was then heated to 180°C at 0.3 kPa (3 mbar) top pressure with mixing by a magnetic stirrer. After 1.5 h, a distillate flow is established, where the distillate was initially collected at the top of the column for 1 h under total reflux at a top pressure of 0.3 kPa (3 mbar).
    [00171] Over the following days, in a total experimental time of 156 h, at an average reflux ratio of 30, a total of 17 distilled fractions were withdrawn. The reflux ratio in this case varied between 15 and 40, so that the maximum temperature remained constant at 134°C. It was ensured by varying the reflux rate that no more product was removed from the reaction mixture than was formed by the reaction. The fractions and their composition can be obtained from Table 1. By means of the continuous withdrawal of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1), the bottom temperature was also kept constant at 180°C. Therefore, the system is not depleted of 3-methylcyclopentadecane-1,5-diol (II.1), and as many equivalents of 3-methylcyclopentadecane-1,5-diol (II.1) have been replaced as taken from 14 -methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) and by-products. The addition of 3-methylcyclopentadecane-1,5-diol (II.1) was pulsed (in portions). As the amount of distillate withdrawn was slowly decreased, an additional 2.25 g of catalyst was added to the reactor after 24 and 89 hours in each case. The concentrations established in the reactor can be taken from Table 2. After 104 h, no more 3-methylcyclopentadecane-1,5-diol (II.1) was replaced and the residual 3-methylcyclopentadecane-1,5-diol (II. 1 ) was converted to 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1). Throughout the experiment, an 80% yield of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) was apparent, based on 3-methylcyclopenta-decane-1,5-diol (II.1 ). In total, 383 g of starting material having a 3-methylcyclopentadecane-1,5-diol content of 93.7% were fed. Table 5: Fractions overview. All concentration data are % area per GC.
    a) = no longer substituted 3-methylcyclopentadecane-1,5-diol (II.1) Table 6: Overview of concentrations in the reactor. All data are % area per GC.
    权利要求:
    Claims (15)
    [0001]
    1. Method for preparing compounds of general formula (I)
    [0002]
    2. Method according to claim 1, characterized in that R1 is hydrogen or methyl, particularly methyl.
    [0003]
    3. Method according to claim 1 or 2, characterized in that the reaction in step b) comprises a first stage, during which the fraction not comprising the compound of formula (I) is separated from the feed mixture by distillation .
    [0004]
    4. Method according to any one of claims 1 to 3, characterized in that the vapor pressure of the solvent used in step b) is lower than the vapor pressure of diol (II).
    [0005]
    5. Method according to any one of claims 1 to 3, characterized in that the vapor pressure of the solvent used in step b) is between the vapor pressure of compound (I) and the vapor pressure of compound (II) ).
    [0006]
    6. Method according to any one of claims 1 to 3, characterized in that the vapor pressure of the solvent used in step b) is between the vapor pressure of compound (I) and the vapor pressure of compound (III) )
    [0007]
    7. Method according to any one of the preceding claims, characterized in that the solvent used in step b) is selected from - aliphatic, cycloaliphatic and aromatic hydrocarbons, - aliphatic, cycloaliphatic and monohydric and polyhydric aromatic alcohols - ether alcohols, polyether polyols and mono- and dialkyl ethers thereof, aromatic ethers and open-chain aliphatic ethers, - ketones, - esters - mixtures thereof.
    [0008]
    Method according to any one of the preceding claims, characterized in that the solvent used in step b) is selected from - C10-C30-alkanes, - C6-C30-alkanols, - C2-C30-alkanediols, - polyalkylene glycols and mono- and dialkyl ethers thereof, - mixtures thereof.
    [0009]
    A method according to any one of claims 1 to 8, characterized in that the compound of formula (I.1) is separated from the reaction mixture in step c) by one-stage distillation and the separated product comprises the following compounds, based in each case on the total weight of the separated product: 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1): 75 - 95% by weight, 3-methylcyclopentadecane-1,5-diol (II.1): 0 - 5% by weight, 3-methylcyclopentadecane-1,5-dione (III.1): 1 - 10% by weight, 14-methyl-16-oxabicyclo[10.3.1]hexadecane (VI .1): 0-15% by weight.
    [0010]
    10. Method according to any one of claims 1 to 8, characterized in that the separation in step c) comprises fractional distillation.
    [0011]
    11. Method according to claim 10, characterized in that at least one distillation column having at least 10 theoretical plates is used for the distillation separation of a fraction comprising the compound of formula (I) in step c).
    [0012]
    12. Method according to claim 10 or 11 for preparing 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1), characterized in that the compound of formula (I) is separated from the mixture of reaction in step c) by fractional distillation and the separated product comprises the following compounds, based in each case on the total weight of the separated product: - 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1): 80 - 99% by weight, - 3-methylcyclopentadecane-1,5-diol (II.1): 0 - 5% by weight, - 3-methylcyclopentadecane-1,5-dione (III.1): 0 to 5% by weight weight, preferably 0 to 1% by weight, - 14-methyl-16-oxabicyclo[10.3.1]hexadecane (VI.1): 0 to 15% by weight, preferably 0 to 10% by weight , - solvent: 0 to 5% by weight, preferably 0 to 1% by weight, - 3-methylcyclopentadecan-5-ol-1-one (VII.1): 0-5% by weight.
    [0013]
    Method according to any one of the preceding claims, characterized in that the solvent content of the reaction mixture in step b) is always maintained at at least 20% by weight, preferably at least 30% by weight, in particular at least 50% by weight, based on the total weight of the reaction mixture in the reaction zone.
    [0014]
    Method according to any one of the preceding claims, characterized in that additionally d) the compounds of the general formula (I) are subjected to a reaction to obtain at least one compound of the general formula (IV).
    [0015]
    15. Method according to claim 14, characterized in that in addition e) the compounds of the general formula (IV) are subjected to hydrogenation to obtain the compound of the general formula (V). where R1 is hydrogen or C1-C4-alkyl.
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    同族专利:
    公开号 | 公开日
    US10259822B2|2019-04-16|
    BR112018010389A2|2018-11-21|
    MX2018006392A|2018-09-05|
    CN108290901A|2018-07-17|
    JP2018535982A|2018-12-06|
    JP6965244B6|2021-12-08|
    ES2861454T3|2021-10-06|
    JP6965244B2|2021-11-10|
    EP3380477B1|2021-01-06|
    WO2017089327A1|2017-06-01|
    US20180346478A1|2018-12-06|
    EP3170828A1|2017-05-24|
    CN108290901B|2021-10-08|
    EP3380477A1|2018-10-03|
    BR112018010389A8|2019-02-26|
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    法律状态:
    2020-03-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-08-24| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    2021-11-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2022-01-04| B09W| Correction of the decision to grant [chapter 9.1.4 patent gazette]|Free format text: REFERENCIA: RPI 2652 DE 03.11.2021 - CODIGO 9.1 |
    2022-01-18| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/11/2016, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
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    EP15195836.0A|EP3170828A1|2015-11-23|2015-11-23|Method for the preparation of compounds with 16-oxabicyclo [10.3.1] pentadecen scaffold and their secondary products|
    EP15195836.0|2015-11-23|
    PCT/EP2016/078385|WO2017089327A1|2015-11-23|2016-11-22|Method for the preparation of compounds having a 16-oxabicyclo[10.3.1]pentadecene scaffold and the subsequent products thereof|
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