Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/01—Preparation of ethers
  • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/01—Preparation of ethers
  • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
  • C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/78—Separation; Purification; Stabilisation; Use of additives
  • C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
  • C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated

Definitions

• the present invention relates to a process for the preparation of a compound of the formula
• Ri is an alkyl radical having 1 to 4 carbon atoms and wherein an intermediate, the compound of formula (I)
• the present invention relates to a process for the preparation of vanillin via guaiacol as an intermediate.
• Vanillin (3-methoxy-4-hydroxybenzaldehyde) or ethylvanillin, but also iso-propylvillillin, as examples of a compound of the formula (IV) are among the world's most important aroma chemicals. Vanillin ranks second to food additive, behind aspartame.
• Vanillin is also used as a fragrance in the perfume industry and as an intermediate in the pharmaceutical industry. Vanillin can be obtained from natural sources such as lignin or ferulic acid, with a significant proportion being produced synthetically. The main part of these synthesis processes is via the intermediate guaiacol (2-methoxyphenol).
• GB 2 252 556 A discloses a process for the preparation of 2-methoxy and 2-ethoxycyclohexanol, in which cyclohexene with hydrogen peroxide, methanol or ethanol and optionally sulfuric acid in the presence of a Catalyst composition, which is prepared by drying and calcination of a mixture of titanium tetraenolate and silica gel in hexane or ethanol is reacted.
• a selectivity of 95% for the target product 2-methoxycyclohexanol is achieved only for the preparation of 2-methoxycyclohexanol, but with the disadvantage that in order to achieve this high selectivity, the addition of sulfuric acid to the reaction mixture is required.
• EG Derouane et al. "Titanium-substituted zeolite beta: an efficient catalyst in the oxy-functionalization of cyclic alkenes using hydrogen peroxide in organic solvents" New J. Chem., 1998, pages 797-799 discloses a process for the preparation of 2-alkoxycyclohexanol in which cyclohexene is reacted with hydrogen peroxide and an alkyl alcohol selected from the group consisting of methanol, ethanol, propanol, isopropyl alcohol and ferf-butanol in the presence of a Ti-Al-beta zeolite catalyst.
• WO 2014/016146 A1 describes a process for the preparation of vanillin from 1, 2-dihydroxybenzene.
• CN 103 709 018 A describes the preparation of guaiacol from cyclohexene oxide by reaction with methanol and subsequent dehydrogenation.
• Ri is an alkyl group having 1 to 4 carbon atoms.
• a special zeolitic material of the framework MWW is used as a catalyst, which has a high selectivity with respect to the target product, the compound of formula (I).
• the present invention relates to a process for the preparation of a compound of the formula (IV)
• Ri is an alkyl group having 1 to 4 carbon atoms, comprising
• the backbone of the zeolite according to (ii) contains silicon, titanium, boron, oxygen and hydrogen;
• Ri of the compound of the formula (I) and of the alcohol R-OH is an alkyl radical having 1 to 4 carbon atoms, ie having 1, 2, 3, or 4 carbon atoms. According to (i), it is possible that a mixture of two or more alcohols R ⁇ OH is used, which differ in the alkyl radical R ⁇ .
• the radical R 1 may be suitably substituted, wherein R 1 may have one or more substituents, which may be, for example, a hydroxy, chlorine, fluorine, bromine, iodine, nitro or amino radical.
• the alkyl radical R- is an unsubstituted alkyl radical, preferably selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, and tert-butyl, more preferably from the group consisting of methyl , Ethyl, n-propyl, and iso-propyl, more preferably from the group consisting of methyl and ethyl. More preferably, R 1 is methyl.
• composition of the liquid mixture according to (i) is not subject to any particular restriction
• the molar ratio cyclohexene: F ⁇ OH may be less than, equal to or greater than 1: 1. It is preferred that in the liquid mixture provided according to (i) before the reaction according to (ii), the molar ratio cyclohexene: F ⁇ OH is at most 1: 1.
• the molar ratio cyclohexene: F ⁇ OH in the according to (i) provided liquid mixture prior to the reaction according to (ii) in the range of 1: 1 to 1: 50, more preferably from 1: 3 to 1: 30, further preferably from 1: 5 to 1:10.
• a solvent may be included in the liquid mixture provided in (i).
• a solvent is present, this is preferably selected from the group consisting of C 1 -C 6 -alkylnitriles, ie C 1, C 2 , C 3, C 4, C 5 or C 6 -alkylnitriles, dialkyl ketones of the formula R 2 -CO-R 3 in which R 2 and R 3 are each independently selected from the group consisting of C 1 -C 6 -alkyl, ie C 1, C 2, C 3, C 4, C 5 or C 6 -alkyl, and a mixture of two or more thereof, more preferably selected from the group consisting of C 1 -C 3 -alkynitriles, ie C 1 -, C 2 - or C 3 -alkylnitriles, dialkyl ketones of the formula R 2 -CO-R 3 , where R 2 and R 3 are each independently selected from the group consisting of C1-C3-alkyl, ie C1-, C2- or C3-alkyl, and a mixture of
• the molar ratio of solvent: cyclohexene may in principle be less than, equal to or greater than 1: 1. It is preferred that in the liquid mixture provided according to (i) before the reaction according to (ii), the molar ratio of solvent: cyclohexene is at least 1: 1. More preferably, the molar ratio of solvent to cyclohexene in the liquid mixture prepared according to (i) before the reaction according to (ii) is in the range from 20: 1 to 1: 1, more preferably from 15: 1 to 1: 1, more preferably from 10: 1 to 1: 1. If the mixture contains as solvent a mixture of two or more solvents, the molar ratio of solvent: cyclohexene refers to the mixture of solvents.
• the mixture provided according to (i) contains no solvent.
• the liquid mixture provided according to (i) preferably consists of at least 90% by weight, more preferably at least 95% by weight, more preferably at least 98% by weight, further preferably at least 99% by weight. more preferably at least 99.5% by weight, more preferably at least 99.9% by weight, of cyclohexene, R 1 0, methanol, hydrogen peroxide and optionally water, if hydrogen peroxide is in the form of an aqueous solution as described below; is used.
• the temperature at which the liquid mixture according to (i) is provided is basically not limited. It is preferable that the liquid mixture according to (i) is provided at a temperature in the range of 5 to 50 ° C, more preferably 10 to 40 ° C, further preferably 15 to 30 ° C.
• the provision of the liquid mixture according to (i) is not subject to any particular restriction.
• the liquid mixture according to (i) can be provided by mixing the cyclohexene, the alcohol R 1 OH, the hydrogen peroxide and optionally the solvent in any order. It is preferred to provide the liquid mixture according to (i) by adding the hydrogen peroxide to a mixture containing the cyclohexene, the alcohol R 1 OH and optionally the solvent.
• the mixture containing the cyclohexene, the alcohol R 1 H and the optional solvent at a temperature in the range of 5 to 50 ° C, more preferably 10 to 40 ° C, further preferably 15 to 30 ° C and when the hydrogen peroxide is added, to maintain the temperature of the resulting mixture suitably within the aforementioned temperature ranges.
• the hydrogen peroxide is added as a solution in one or more suitable solvents.
• suitable solvents are, for example, water or organic solvents such as, for example, organic solvents selected from the group consisting of C 1 -C 6 -alcohols, C 1 -C 6 -alkylnitriles, dialkyl ketones of the formula R 2 -CO-R 3 , where R 2 and R 3 are each independently from the group consisting of C1-C6 alkyl, and a mixture of two or more thereof, preferably from the group consisting of C1-C3-alcohols, C1-C3 alkynitriles, dialkyl ketones of the formula R 2 -CO-R 3 , wherein R 2 and R 3 are each independently selected from the group consisting of C 1 -C 3 alkyl, and a mixture of two or more thereof, more preferably selected from the group consisting of methanol, acetonitrile, acetone and a mixture thereof.
• the hydrogen peroxide is preferably added in the form of a methanolic or aqueous, preferably aqueous solution.
• the content of the preferred aqueous solution of hydrogen peroxide is not particularly limited, and is preferably in the range of 25 to 75% by weight, more preferably 40 to 70% by weight, based on the total weight of the aqueous solution.
• the molar ratio of cyclohexene: hydrogen peroxide may be less than, equal to or greater than 1: 1. It is preferred that in the liquid mixture provided according to (i) before the reaction according to (ii) the cyclohexene: hydrogen peroxide molar ratio is at least 1: 1.
• the mixture provided according to (i) preferably contains no strong non-nucleophilic inorganic acid, preferably no sulfuric acid.
• the catalyst used in (ii) has a high selectivity with respect to the target product 2-alkoxycyclohexanol.
• the catalyst used in (ii) is not particularly limited.
• the zeolitic material of the framework structure MWW has at least one of the following features according to the listed embodiments, including the combinations of embodiments according to the stated dependencies:
• Zeolitic material of the framework structure MWW wherein the framework of the zeolitic material contains boron and titanium, wherein preferably at least 99 wt .-%, more preferably at least 99.5 wt .-%, more preferably at least 99.9 wt .-% of Skeleton of the zeolitic material of silicon, titanium, boron, oxygen and hydrogen.
• a zeolitic material according to Embodiment 1 wherein the molar ratio B: Si is in the range of 0.02: 1 to 0.5: 1, preferably 0.05: 1 to 0.15: 1, and the molar ratio of Ti: Si in the range of 0.01: 1 to 0.05: 1, preferably 0.017: 1 to 0.025: 1.
• a zeolitic material according to embodiment 1 or 2 wherein the zeolitic material is in the calcined state.
• a zeolitic material according to Embodiment 3 wherein the calcined state of the zeolitic material is achieved by calcining the zeolitic material in its uncalcined state at a temperature in the range of 500 to 700 ° C, more preferably 550 to 700 ° C, more preferably from 600 to 700 ° C, preferably within a period in the range of 0.1 to 24 hours, more preferably from 1 to 18 hours, more preferably from 6 to 12 hours, preferably in an oxygen-containing atmosphere.
• TOC total organic carbon
• Spectrum of zeolitic material includes:
• the ratio of the integral of the range of the first signal to the integral of the range of the third signal preferably in the range of 0.6 to 1, 1, more preferably from 0.7 to 1, 0, more preferably from 0.8 to 0, 9 lies.
• a zeolitic material according to any of embodiments 1 to 6, wherein the 11 B-NMR spectrum of the zeolitic material comprises:
• a second signal in the range of 10.0 to 1.0 ppm, preferably with a peak in the range of 6.5 to 5.5 ppm, more preferably 6.2 to 5.8 ppm,
• a third signal in the range of 1.0 to -7.0 ppm, preferably with a peak in the range of -2.4 to -3.4 ppm, more preferably from -2.7 to -3.1 ppm,
• the ratio of the integral of the range of the third signal to the integral of the range of the second signal preferably in the range of 1, 00 to 1, 15, more preferably from 1, 05 to 1, 15, more preferably from 1, 10 to 1, 15 lies.
• BET specific surface area
• Zeolitic material according to any one of embodiments 1 to 9, wherein the infrared spectrum of the zeolite material has a band at (3748 ⁇ 20) cm "1, a band at (3719 ⁇ 20) cm" 1, a band at (3689 ⁇ 20) cm “ 1 , a band at (3623 ⁇ 20) cm -1 , a band at (3601 ⁇ 20) cm -1, and a band at (3536 ⁇ 20) cm -1 . 1 1.
• Zeolitic material according to embodiment 11 characterized by an X-ray diffractogram, which additionally peaks at 2 theta angles of (7.0 ⁇ 0.1) °, (8.1 ⁇ 0.1) °, (10.1 ⁇ 0 , 1) °, (14.3 ⁇ 0.1) °, (20.4 ⁇ 0.1) °, (21, 9 ⁇ 0.1) °, (28.9 ⁇ 0.1) °, ( 33.8 ⁇ 0, 1) °, (47.0 ⁇ 0.1) °, (65.4 ⁇ 0.1) °, (66.4 ⁇ 0.1) °.
• A providing an aqueous synthesis mixture comprising a silicon source, a boron source, a titanium source and a MWW template compound, wherein the temperature of the aqueous synthesis mixture is at most 50 ° C; (b) heating the aqueous synthesis mixture provided according to (a) from the temperature of at most 50 ° C to a temperature in the range of 160 to 190 ° C within a time of at most 24 hours;
• Framework MWW to give the zeolite of the framework MWW.
• zeolitic material of embodiment 18 or 19, wherein the aqueous mixture containing the boron source, the titanium source, and the MWW template compound is prepared by adding a mixture containing a portion of the MWW template compound and the silicon source to an aqueous mixture containing a portion of the MWW Templattress and the boron source, wherein the mixture containing a portion of the MWW template compound and the titanium source preferably contains no water.
• the boron source is selected from the group consisting of boric acid, borates, boron oxide and a mixture of two or more thereof, preferably from the group consisting of boric acid, borates and a mixture thereof, the boron source more preferably boric acid;
• the titanium source is selected from the group consisting of titanium alkoxides, titanium halides, titanium salts, titanium dioxide and a mixture of two or more thereof, preferably from the group consisting of titanium alkoxides, titanium halides and a mixture thereof, the titanium source more preferably a titanium alkoxide, more preferably titanium tetrabutoxide is;
• the MWW template compound is selected from the group consisting of piperidine, hexamethyleneimine, N, N, N, N ', N', N'-hexamethyl-1, 5-pentanediammonium salts, 1, 4-bis (N-methylpyrrolidinyl) butane, Octyltrimethylammonium hydroxide, Heptyltrimethylammonium- hydroxide, hexyltrimethylammonium hydroxide and a mixture of two or more thereof, preferably from the group consisting of piperidine, hexamethyleneimine and a mixture thereof, wherein the MWW template compound is more preferably piperidine.
• the boron source calculated as elemental boron, based on the silicon source, calculated as elemental silicon, in a molar ratio ranging from 0.18: 1 to 5.2: 1, preferably from 0.5: 1 to 3: 1;
• the titanium source calculated as elemental titanium, based on the silicon source, calculated as elemental silicon, in a molar ratio ranging from 0.005: 1 to 0.15: 1, preferably from 0.01: 1 to 0.1: 1;
• the MWW template compound based on the silicon source calculated as elemental silicon, in a molar ratio ranging from 0.4: 1 to 4.2: 1, preferably from 0.6: 1 to 2: 1;
• the water based on the silicon source, calculated as elemental silicon, in a molar ratio in the range of 1: 1 to 30: 1, preferably from 2: 1 to 25: 1.
• Framework structure MWW preferably at a temperature in the range of 10 to 150 ° C, more preferably from 30 to 130 ° C, preferably in an oxygen-containing atmosphere.
• a zeolitic material according to any one of embodiments 18 to 34 wherein before (f) the zeolitic material of the framework MWW is not treated with an aqueous solution having a pH of at most 6 as determined by a pH-sensitive glass electrode, and wherein according to Steps (f) and (g) the shaped body containing the zeolitic material of the framework structure MWW is not treated with an aqueous solution having a pH of at most 6, determined by means of a pH-sensitive glass electrode.
• the mass ratio hydrogen peroxide: zeolitic material of the framework MWW at the beginning of the reaction according to (ii) in the range of 10: 1 to 0.1: 1, preferably from 1: 1 to 0 , 2: 1, more preferably from 0.75: 1 to 0.25: 1.
• the reaction according to (ii) can generally be carried out according to all suitable process procedures. Thus, for example, a discontinuous procedure in one or more batch reactors or a continuous procedure in one or more, optionally connected in series and / or parallel, continuously operated reactors possible.
• the implementation of the reaction according to (ii) in a discontinuous procedure is not subject to any particular restriction.
• a suitable reactor for the reaction according to (ii) for example, a reactor equipped with suitable heating means, a suitable stirrer and a reflux condenser can be used.
• the reaction according to (ii) is preferably carried out in an open system.
• the reaction according to (ii) is carried out with suitable agitation of the reaction mixture such as, for example, stirring, wherein the energy input by the agitation during the reaction can be kept substantially constant or changed.
• the energy input can be suitably selected depending on, for example, the volume of the reaction mixture, the form of the catalyst or the reaction temperature.
• a zeolitic material having skeleton structure MWW as described above in Embodiments 1 to 15 and 18 to 33 is preferably used.
• a fixed-bed catalyst is preferably used in the context of the continuous mode of operation, as catalyst (ii) preferably a shaped body as described above in embodiments 16, 17 and 34 to 36, containing the zeolitic material with framework structure MWW and preferably at least one binder material, preferably silica, used.
• the catalyst loading is preferably in the range of 0.05 to 5 mol / kg / h, more preferably from 0.1 to 4 mol / kg / h, more preferably from 0.2 to 3 mol / kg / h, wherein the catalyst loading is defined as mol (hydrogen peroxide) / kg (zeolitic material of the framework MWW) / h.
• the mixture according to (i) is preferably provided as a liquid stream which is passed into the one or more reactors where it is subjected to the reaction conditions according to (ii).
• the individual components of the mixture according to (i) in the form of two or more streams, which may contain the individual components or mixture thereof, into the one or more reactors where the individual streams after the Reactor input to the mixture according to (i) are merged.
• two or more can be connected in parallel and / or two or more connected in series.
• One or more intermediate stages can be provided between two reactors connected in series, for example for intermediate removal of desired product.
• Next can be between two series connected Reactors of one or more of the starting materials cyclohexene, alcohol R 1 OH, hydrogen peroxide and optional solvent can be supplied.
• the reaction according to (ii) can be carried out using one or more catalysts different from one another and comprising a zeolitic material of the framework MWW and containing B and Ti in the framework.
• the catalysts may differ, for example, with regard to the chemical composition or the manner of preparation of the zeolitic material of the framework MWW.
• the catalysts may be used in the case of moldings, for example as regards the properties of the molding, e.g. differ by the geometry of the shaped body, the porosity of the shaped body, the binder content of the shaped body, the binder material or the content of zeolitic material of the framework structure MWW.
• the reaction according to (ii) is preferably carried out in the presence of a single catalyst according to the invention.
• the catalyst used is separated from the mixture containing the compound of formula (I). If the reaction is carried out in a continuous procedure, for example in a fixed bed reactor, separation of the catalyst can be dispensed with, since the reaction mixture leaves the reactor and the catalyst remains in the fixed bed reactor.
• the catalyst which is preferably used in the form of a powder, can be separated by a suitable separation method, for example filtration, ultrafiltration, diafiltration, centrifugation and / or decantation. After separation, the separated catalyst may be subjected to one or more washing steps with one or more suitable washing liquids.
• washing liquids examples include water, ethers, such as dioxane, for example 1,4-dioxane, alcohols, for example methanol, ethanol, propanol, or a mixture of two or more thereof. Dioxanes are preferably used as washing liquid.
• the washing step is preferably carried out at a temperature in the range of 10 to 50 ° C, more preferably 15 to 40 ° C, further preferably 20 to 30 ° C.
• the conversion, the selectivity, or both the conversion and the selectivity which the catalyst according to the invention offers fall below certain values, it is possible to suitably regenerate the catalyst, for example by washing with one or more suitable detergents, or by drying one or more suitable atomic spheres, at one or more suitable temperatures and at one or more suitable pressures, or by calcining in one or more suitable atomic spheres, at one or more suitable temperatures and at one or more suitable pressures, or by a combination of two or more of these measures, each of which may be carried out once or more times within one or more suitable periods.
• the reaction according to (ii) is preferably carried out at a temperature of the reaction mixture in the range from 40 to 150.degree. C., more preferably from 50 to 125.degree. C., more preferably from 70 to 100.degree.
• the reaction according to (ii) is preferably carried out, if the reaction is carried out batchwise, for example as a batch reaction, at the boiling point of the liquid mixture, more preferably under reflux.
• the duration of the reaction according to (ii), the reaction should be carried out batchwise, for example as a batch reaction, in the range of 1 to 12 h, more preferably from 1, 5 to 10 h, more preferably from 2 to 8 h ,
• the term "at the beginning of the reaction” generally refers to the time at which all starting materials, including the catalyst, are present simultaneously in the reaction mixture and, depending on the temperature, the reaction of the
• the term "at the beginning of the reaction” generally refers to the time at which the mixture provided according to (i) contacts the catalyst.
• the molar content of the mixture obtained from the reaction according to (ii) on the compound of the formula (I), based on the sum of the molar contents of the mixture obtained from the reaction according to (ii), of the compounds of the formulas (I) is preferably (Ib), (Ic), (Id) and (le)
• each of the compounds (Ib), (Ic), (Id) and (le) is present in the mixture obtained according to (ii); Rather, the mixture obtained according to (ii), in addition to the compound (I), only one, only two, only three or all four of the compounds (Ib), (Ic), (Id) and (le).
• the mixture obtained in (ii) containing the compound of the formula (I) is preferably worked up to separate the compound of the formula (I). If the conversion of hydrogen peroxide during the reaction is not complete, it is preferable to use before Workup to remove the unreacted hydrogen peroxide contained in the mixture, for example by addition of suitable substances, for example by means of quenching to decompose.
• suitable substances for example by means of quenching to decompose.
• suitable substances for example, tertiary amines, polyamines, salts of heavy metals such as iron, manganese, cobalt and vanadium, sulfinic acids, mercaptans, dithionites, sulfites and strong acids and bases are suitable for the decomposition of the excess hydrogen peroxide.
• the decomposition of the excess hydrogen peroxide is preferably carried out by means of an alkali metal or alkaline earth metal sulfite, more preferably alkali metal sulfite, more preferably sodium sulfite.
• preference is given to at least 95%, more preferably at least 97%, more preferably at least 99%, more preferably at least 99.5%, even more preferably at least 99.9%, of the unreacted hydrogen peroxide from the mixture obtained from the reaction according to (ii) away.
• a mixture comprising an aqueous phase and an organic phase.
• all batch methods or continuous methods known to those skilled in the art are applicable.
• the thus separated organic phase is then used as the mixture obtained in (iii) in (iii).
• the mixture obtained according to (ii) for example the organic phase separated as described above, in addition to the compound of formula (I), the compound of formula (Ib)
• the compound of the formula (I) is appropriately separated from the mixture obtained in (ii) to obtain a mixture concentrated with respect to the compound of the formula (I).
• Suitable separation methods for this separation of the compound of the formula (Ib) are those in which distillative removal is preferred.
• a mixture concentrated with respect to the compound of the formula (I) which contains at least 95% by weight, preferably more than 95% by weight, for example at least 96% by weight or at least 97% by weight or at least 98% by weight or at least 99% by weight of the compound of the formula (I).
• the separation of the compound of the formula (Ib) and the separation of the aqueous phase can be carried out in a single step by means of this distillative separation.
• preferred distillation conditions to be used can be adapted by the skilled person in a simple manner to the particular separation problem, that is, for example, to the boiling points of the compounds of the formulas (I) and (Ib).
• preferred distillation conditions are for example a bottom temperature in the range of 85 to 95 ° C and a top pressure in the range of 15 to 25 mbar.
• the mixture obtained by the separation and concentrated with respect to the compound of formula (I) is preferably mixed with water.
• This aqueous mixture thus obtained is then fed to the dehydrogenation in (iv).
• the dehydrogenation according to (iv) can in principle be carried out in the mixture obtained according to (iii), preferably in the aqueous mixture obtained according to (iii). It is preferable to suitably bring the mixture obtained according to (iii), preferably the aqueous mixture obtained according to (iii), into the gas phase before the dehydrogenation and to carry out a gas-phase hydrogenation according to (iv). Therefore, it is preferred to evaporate the mixture obtained according to (iii) with respect to the compound of formula (I), preferably the aqueous mixture, before dehydrogenation according to (iv).
• Preferred temperatures at which this evaporation is carried out are in the range from 175 to 375 ° C, preferably from 225 to 325 ° C, more preferably from 250 to 300 ° C.
• evaporation it is possible in principle to use any known and known evaporator suitable for this purpose by a person skilled in the art.
• the thus preferably evaporated mixture is then fed to the dehydrogenation according to (iv), this feed preferably being carried out by means of a carrier gas.
• Preferred carrier gases are those which are inert or substantially inert during dehydrogenation according to (iv).
• the carrier gas is selected from the group consisting of hydrogen, nitrogen, argon, carbon monoxide, water vapor and a A mixture of two or more thereof, more preferably selected from the group consisting of hydrogen, nitrogen, argon, carbon monoxide and a mixture of two or more thereof, more preferably selected from the group consisting of hydrogen, nitrogen, argon and a mixture of two or more thereof , Further preferred is a carrier gas which comprises hydrogen and nitrogen and more preferably at least 95% by volume, more preferably at least 98% by volume, more preferably at least 99% by volume of hydrogen and nitrogen. More preferably, the volume ratio nitrogen: hydrogen is in the range from 2: 1 to 20: 1, more preferably in the range from 5: 1 to 10: 1. Preferably both the evaporation and the dehydrogenation are carried out continuously in accordance with the invention.
• the dehydrogenation is carried out in the presence of a heterogeneous catalyst with which the mixture to be dehydrogenated is contacted.
• a heterogeneous catalyst with which the mixture to be dehydrogenated is contacted.
• the heterogeneous catalyst is arranged as a catalyst bed, more preferably as a fixed catalyst bed.
• the dehydrogenating component of the catalyst used is preferably a dehydrogenating noble metal, which is more preferably selected from the group consisting of Pd, Rh, Pt and a combination of two or more thereof.
• the dehydrogenating component of the catalyst preferably the dehydrogenating noble metal, is suitably supported.
• the support material there are no particular limitations, as long as it is ensured that the support material during the dehydrogenation substantially inert or the dehydrogenation favoring behaves.
• the support material is selected from the group consisting of activated carbon, alumina, silica and a combination of two or more thereof.
• a catalyst which is preferred according to the present invention comprises activated carbon as the dehydrogenating component Pd and as support material, the content of palladium in the catalyst preferably being in the range from 1 to 10% by weight, more preferably in the range from 2 to 8% by weight, more preferably in Range of 3 to 7% by weight, based in each case on the total mass of the catalyst.
• a catalyst which is likewise preferred according to the present invention comprises activated carbon as the dehydrogenating component Pd and as support material, the content of the Catalyst on palladium preferably in the range of 0.1 to 5% by weight, more preferably in the range of 0.2 to 3% by weight, more preferably in the range of 0.5 to 2% by weight, based in each case on the total mass of the catalyst.
• the heterogeneous catalyst is suitably activated prior to dehydrogenation according to (iv). In the context of this activation, it is preferable to purge the catalyst with a gas, preferably at elevated temperature compared to room temperature.
• the gas used for purging is selected from the group consisting of hydrogen, nitrogen, argon and a mixture of two or more thereof, more preferably from the group consisting of hydrogen, nitrogen, and a mixture thereof.
• Preferred temperatures at which rinsing occurs are in the range of 300 to 550 ° C, more preferably 350 to 500 ° C, further preferably 375 to 450 ° C. These temperatures are understood to be the temperature of the gas or of the gas mixture with which the catalyst is purged.
• Rinsing of the catalyst can in principle be done outside the reactor used for dehydrogenation.
• the catalyst is rinsed in the reactor which is used for dehydrogenation.
• the catalyst Before or after this rinsing, preferably before rinsing, the catalyst may be suitably washed, washing with an aqueous solution containing a base, preferably a hydroxide, more preferably an alkali metal hydroxide, more preferably potassium hydroxide, being preferred.
• a base preferably a hydroxide, more preferably an alkali metal hydroxide, more preferably potassium hydroxide
• the reactor used for dehydrogenation and containing the catalyst with a gas which is preferably selected from the group consisting of nitrogen, argon and a mixture thereof, more preferably nitrogen , more preferably is technical nitrogen.
• the temperature at which the dehydrogenation according to (iv) is carried out is preferably in the range of 200 to 400 ° C, more preferably 250 to 350 ° C, further preferably 275 to 325 ° C. This temperature is understood to be the temperature of the catalyst used for dehydrogenation. If the catalyst is preferably present as a catalyst bed, more preferably as a fixed catalyst bed, this temperature is understood to be the temperature of the fixed catalyst bed.
• the compound of the formula (II) is preferably separated before the formylation according to (v) to obtain a mixture concentrated with respect to the compound of the formula (II).
• Suitable separation methods for this separation of the compound of the formula (II) are suitable, with distillative removal being preferred.
• a mixture concentrated with respect to the compound of the formula (II) containing at least 95% by weight, preferably more than 95% by weight, for example at least 96% by weight or at least 97% by weight or at least 98% by weight or at least 99% by weight of the compound of formula (II).
• preferred distillation conditions to be used can be easily adapted by the skilled person to the particular separation problem.
• preferred distillation conditions are a bottom temperature in the range of 55 to 80 ° C and a top pressure in the range of 0.5 to 5 mbar.
• the mixture concentrated according to the compound of the formula (II) is separated off at the top of the column.
• Step M According to (v), the compound of the formula (II) contained in the mixture obtained according to (iv) is formylated to obtain a mixture containing the compound of the formula (IV).
• this formylation can be carried out according to any suitable method.
• the present invention relates to the process as described above, wherein the formylation according to (v) comprises: (v-1) reacting the compound of the formula (II) present in the mixture obtained according to (iv) with glyoxylic acid OHC-COOH, preferably in the aqueous phase, to obtain a mixture comprising a compound of the formula (III)
• the reaction according to (v-1) takes place in the basic medium.
• the reaction mixture contains a Bronsted base which is preferably selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides and a mixture of two or more thereof, more preferably from the group consisting of alkali metal hydroxides and a mixture of two or more from that. More preferably, the reaction mixture contains sodium hydroxide.
• an aqueous solution containing glyoxylic acid which more preferably contains a Bronstedt base, which is preferably selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides and a mixture of two or more thereof, more preferably from the group consisting of alkali metal hydroxides and a mixture of two or more thereof, the Bronsted base more preferably comprising sodium hydroxide, more preferably sodium hydroxide.
• a Bronstedt base which is preferably selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides and a mixture of two or more thereof, more preferably from the group consisting of alkali metal hydroxides and a mixture of two or more thereof, the Bronsted base more preferably comprising sodium hydroxide, more preferably sodium hydroxide.
• This aqueous solution is then preferably mixed with an aqueous solution containing the mixture obtained according to (iv) and preferably a Bronsted base, which is preferably selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides and a mixture of two or more thereof preferably selected from the group consisting of alkali metal hydroxides and a mixture of two or more thereof, the Bronsted base more preferably comprising sodium hydroxide, more preferably sodium hydroxide.
• a Bronsted base which is preferably selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides and a mixture of two or more thereof preferably selected from the group consisting of alkali metal hydroxides and a mixture of two or more thereof, the Bronsted base more preferably comprising sodium hydroxide, more preferably sodium hydroxide.
• the molar ratio of Bronstedt base, more preferably sodium hydroxide, to the sum of the compound of formula (II) and glyoxylic acid in the range of 0.2: 1 to 2: 1, is preferred from 0.5: 1 to 1, 5: 1, more preferably from 0.75: 1 to 1, 25: 1.
• the reaction according to (v-1) preferably takes place at a temperature of the reaction mixture in the range from 10 to 40 ° C., more preferably in the range from 15 to 35 ° C., more preferably in the range from 20 to 30 ° C. More preferably, the reaction mixture is suitably stirred.
• the pH of the mixture obtained after the reaction of (v-1) is preferably in the range of 9.5 to 12.5, more preferably 10 to 12, further preferably 10.5 to 11.5.
• the mixture obtained according to (v-1) is preferably purified in a further step, whereby a mixture is obtained which is concentrated with respect to the compound of formula (III).
• this purification is carried out so that the resulting mixture purified with respect to the compound of formula (III) is an aqueous mixture. Therefore, the present invention relates to the process as described above, wherein the formylation according to (v) additionally comprises:
• this purification comprises extraction with one or more suitable organic solvents, more preferably comprising toluene. It is further preferred according to the invention to extract the mixture obtained according to (v-1) with toluene. Preference is given to extracting unreacted compound of the formula (II) from the aqueous phase. The thus separated compound of the formula (II) can then be advantageously recycled to the process according to the invention as starting material for the formylation according to (v). Therefore, the present invention relates to the process as described above, wherein the purification according to (v-2) comprises an extraction, preferably an extraction with an organic solvent, preferably comprising toluene.
• the pH of the mixture is adjusted to a value in the range of 0.5 to 1.5. It is further preferred that the pH is adjusted to a value in the range from 0.5 to 1.5 in two or more steps, preferably in two steps.
• the pH of the mixture after this first step is in the range of 4.0 to 5.0.
• the pH value is understood here as the pH, as determined by the use of a pH-sensitive glass electrode.
• an aqueous mixture which preferably has a pH in the range of 0.5 to 1.5 and contains the compound of the formula (III).
• the compound of the formula (III) present in the mixture obtained according to (v-1), preferably according to (v-2), according to the invention is preferably subjected to an oxidative decarboxylation in a further step to give a mixture which comprises the compound of the formula ( IV). Therefore, the present invention relates to the process as described above, wherein the formylation according to (v) additionally comprises:
• the aqueous mixture obtained according to (v-1), preferably according to (v-2), is mixed with one or more organic solvents, preferably comprising toluene, so that the in (v-3) used mixture containing the compound of formula (III), an aqueous-organic mixture.
• the oxidative decarboxylation according to (v-3) takes place in the presence of an oxidizing agent. All suitable oxidizing agents can be used in principle.
• the oxidizing agent is selected from the group consisting of CuO, Pb0 2 , Mn0 2 , Co 3 0 4 , HgO, Ag 2 0, Cu (II) salts, Hg (II) salts, Fe (III) salts, Ni (III) salts, Co (III) salts, chlorates and a mixture of two or more thereof, preferably selected from the group consisting of CuO, MnO 2 , Cu (II) salts, Fe (III) salts and a Mixture of two or more of them. More preferably, the oxidative decarboxylation according to (v-3) takes place in the presence of FeCl 3 as the oxidant.
• Preferred temperatures at which the oxidative decarboxylation according to (v-3) is carried out are in the range of 60 to 110 ° C, more preferably 70 to 100 ° C, further preferably 80 to 95 ° C. This temperature is understood as the temperature of the reaction mixture.
• a mixture preferably an aqueous mixture, more preferably an aqueous-organic mixture containing the compound of formula (IV) is obtained.
• This mixture can in principle be used as such for further reactions, if the compound of the formula (IV) present in the mixture, such as, for example, vanillin, ethylvanillin or isopropylvillillin, serve as an intermediate for subsequent synthesis steps and the aqueous or aqueous-organic mixture for this purpose suitable is. Therefore, the present invention also relates to a mixture containing the compound of formula (IV) which is prepared or preparable according to a method as described above comprising (i) to (v), preferably comprising (i) to (v-3).
• Step (vi) It is preferred according to the invention to separate off the compound of the formula (IV) from the mixture obtained according to (v), preferably (v-3), in a suitable manner, and thereby to purify it as preferred. Therefore, the present invention also relates to the method as described above, additionally comprising
• the present invention relates to the process as described above, wherein the mixture obtained according to (v), preferably according to (v-3) comprises water and at least one organic solvent, and wherein (vi) comprises;
• the aqueous phase separated from the organic phase according to the said preferred process is preferably extracted with an organic solvent, preferably comprising toluene, whereby the compound of the formula (IV) still present in the aqueous phase is converted into an organic phase. It is preferred in this case to carry out the extraction at a temperature of the mixture to be extracted of elevated compared to room temperature, the temperature more preferably in the range of 50 to 95 ° C, more preferably from 60 to 95 ° C, more preferably from 70 to 95 ° C, more preferably from 80 to 95 ° C, more preferably from 85 to 95 ° C.
• the at least one organic solvent used preferably contains toluene, more preferably it is toluene. Therefore, the present invention also relates to the method as described above, wherein (vi) additionally comprises:
• this separated organic phase according to (vi-1) or the separated organic phase according to (vi-1) or the combined organic phases according to (vi-1) and (vi-2), containing the compound of formula (IV) is used as such, for example, when the compound of formula (IV) as an intermediate for subsequent Synthesis steps serves.
• the detergent preferably comprising water, more preferably water. It is preferred that this washing is carried out at a temperature of the detergent in the range of 10 to 40 ° C, preferably from 15 to 35 ° C, more preferably from 20 to 30 ° C. Therefore, the present invention also relates to the method as described above, wherein (vi) additionally comprises:
• the preferably washed organic phase containing the compound of formula (IV) is used as such, for example, when the compound of formula (IV) serves as an intermediate for subsequent synthetic steps.
• the compound of the formula (IV) refers to a mixture or a composition which is preferably at least 99% by weight, based on the total weight of the mixture or the composition, of the compound of the Formula (IV) exists.
• concentration under reduced pressure relative to ambient pressure which is preferably in the range from 1 to 100 mbar, more preferably from 1 to 50 mbar, more preferably from 1 to 10 mbar. Therefore, the present invention also relates to the method as described above, wherein (vi) additionally comprises:
• Ri is an alkyl group having 1 to 4 carbon atoms, comprising
• the backbone of the zeolite according to (ii) contains silicon, titanium, boron, oxygen and hydrogen;
• the solvent is selected from the group consisting of C 1 -C 6 -alkylnitriles, dialkylketones of the formula R 2 -CO-R 3 , wherein R 2 and R 3 are each independently selected from the group consisting of C 1 -C 6 -alkyl are selected, and a mixture of two or more thereof, more preferably from the group consisting of C1 -C3 alkynitriles, dialkyl ketones of the formula R 2 -CO-R 3 , wherein R 2 and R 3 are each independently selected from the group consisting of C1 C3 alkyl are selected, and a mixture of two or more thereof.
• liquid mixture according to (i) is provided by adding the hydrogen peroxide to a mixture containing the cyclohexene, the alcohol F OH and optionally the solvent.
• zeolite of the framework MWW is preparable or prepared according to a process comprising (a) providing an aqueous synthesis mixture comprising a silicon source, a boron source, a titanium source and an MWW template compound, wherein the
• Temperature of the aqueous synthesis mixture is at most 50 ° C;
• a process according to embodiment 33 wherein the mixture obtained from the reaction according to (ii) contains unreacted hydrogen peroxide, and wherein (ii) additionally removing at least 99% of the unreacted hydrogen peroxide from the mixture obtained from the reaction according to (ii) includes.
• removing the unreacted hydrogen peroxide comprises quenching the unreacted hydrogen peroxide.
• removing the unreacted hydrogen peroxide comprises quenching the unreacted hydrogen peroxide with sodium sulfite.
• the separation of the compound of formula (I) from the mixture obtained according to (ii) comprises a distillation whereby the product obtained from the distillation, relative to the compound of formula ( I) concentrated mixture has a content of the compound of formula (I) preferably of at least 90 wt .-%, more preferably of at least 95 wt .-%.
• the carrier gas comprises a mixture of hydrogen and nitrogen, preferably at least 95% by volume, more preferably at least 98% by volume, of hydrogen and nitrogen.
• the catalyst is preferably a dehydrogenating noble metal, more preferably a noble metal selected from the group consisting of Pd, Rh, Pt and a Combination of two or more of them.
• the noble metal is preferably supported on at least one support material, which is preferably selected from the group consisting of activated carbon, alumina, silica, and a combination of two or more thereof.
• the activation comprises purging the heterogeneous catalyst with a gas, preferably selected from the group consisting of hydrogen, nitrogen, argon, and a mixture of two or more thereof.
• a gas preferably selected from the group consisting of hydrogen, nitrogen, argon, and a mixture of two or more thereof.
• the purging with the gas is preferably carried out at a temperature of the gas in the range of 350 to 500 ° C, more preferably 375 to 450 ° C.
• Catalyst bed is.
• (vi) additionally comprises: (vi-3) washing the organic phase obtained in (vi-1) or the organic phases obtained in (vi-1) and (vi-2), containing the compound of the formula
• (vi) additionally comprises: (vi-4) concentrating the organic phase obtained in (vi-1) or the organic phases obtained in (vi-1) and (vi-2), preferably, the organic phase washed according to (vi-3) or the organic phases washed according to (vi-3), with respect to the compound of the formula (IV).
• Ri is an alkyl group having 1 to 4 carbon atoms, obtained or obtainable by a
• Reference Example 1 Measurement of 11 B solid-state NMR spectra
• the 11 B solid-state NMR experiments were carried out using a Bruker Avance III spectrometer with 400 MHz 1 H Larmor frequency (Bruker Biospin, Germany). The samples were stored in 4 mm Zr0 2 rotors at 63% relative humidity at room temperature prior to packaging. Measurements were performed at 10 kHz room temperature magic angle spinning
• the 11 B spectra were measured using a 11 B 15 ° excitation pulse of 1 microsecond ( ⁇ ) pulse width, 11 B Carrier frequency, which corresponds to -4 ppm in the referenced spectrum, and a scan waiting time ("scan-recycle delay") of 1 s.
• the signals were acquired for 10 ms and accumulated with 5000 scans.
• the 29 Si solid-state NMR experiments were performed using a Bruker Advance III spectrometer with 400 MHz 1 H Larmor frequency (Bruker Biospin, Germany). The samples were stored in 4 mm Zr0 2 rotors at 63% relative humidity at room temperature prior to packaging. Measurements were performed at 10 kHz room temperature magic angle spinning, and the 29 Si spectra were measured using a 29 Si 90 ° exciter pulse of 5 microseconds ( ⁇ ) pulse width, a 29 Si Carrier frequency, which corresponds to -1 12 ppm in the referenced spectrum, and a scan waiting time ("scan-recycle delay") of 120 s.
• ⁇ microseconds
• the signals were for 20 Milliseconds (ms) acquired at 63 kHz high-power proton decoupling and accumulated for at least 16 hours Spectra were performed using a Bruker topspin with 50 Hz exponential line broadening, phase regulation and baseline correction over the entire The spectra were calculated using glycine with a carbonyl peak at 175.67 ppm as a secondary standard versus 1% TMS in CDCl 3 on the unified IUPAC chemical shift scale (Pure Appl Chem, Vol. P. 59).
• the water adsorption / desorption isotherms were carried out on a VT Instruments VTI SA apparatus which performs a stepwise isotherm program.
• the experiment consisted of a run or series of runs performed on a sample material placed on the microbalance dish in the apparatus. Before starting the measurement, the residual moisture of the sample was removed by heating the sample to 100 ° C (heating rate 5 K / min) and kept under nitrogen flow for 6 hours. After the drying program, the temperature in the cell was reduced to 25 ° C and kept isothermal during the measurement. The microbalance was calibrated and the weight of the dried sample was adjusted (maximum mass deviation 0.01 wt%). Water uptake by the sample was measured as the increase in weight over the dry sample.
• an adsorption curve was measured by increasing the relative humidity (expressed as% by weight of water in the atmosphere of the cell) to which the sample was exposed, and measuring the water absorption of the sample as an equilibrium.
• the relative humidity was increased in increments of 10% by weight from 5% to 85% by weight, and at each step the system controlled the relative humidity and monitored the sample weight until equilibrium conditions were reached after sample 85 % By weight to 5% by weight of relative humidity in 10% by weight increments, and the change in the weight of the sample (water uptake) was monitored and recorded.
• the FT-IR (Fourier Transform Infrared) measurements were performed on a Nicolet 6700 spectrometer.
• the powdered material was pressed into a self-supporting compact without the use of any additives.
• the compact was introduced into a high vacuum cell (HV) housed in the FT-IR instrument.
• HV high vacuum cell
• the spectra were recorded at 50 ° C after the cooling of the cell.
• the spectra were in the range from 4000 to 800 cm" 1 at a resolution of 2 cm "1.
• Reference Example 5 Measurement of X-ray diffraction spectra The X-ray diffraction spectrum was recorded with a Bruker / AXS D8 Advance Series 2 having a multiple sample changer.
• Example 1 Preparation of a zeolite of the framework MWW containing boron
• the mixture had a pH of 11.3.
• the mixture was transferred to a 2.5 liter autoclave and slowly heated to 170 ° C over 10 hours at a heating rate of about 0.2 K / min, and then this temperature was stirred for 160 hours at a stirring speed of 100 U / min held.
• the pressure during the reaction ranged from 8.3 to 9 bar.
• the suspension obtained had a pH of 1 1, 2 on.
• the suspension was filtered and the filter cake was washed with deionized water until the washings had a pH of less than 10.
• the filter cake was dried in a drying oven at 120 ° C for 48 hours, and heated at a heating rate of 2 K / min to a temperature of 650 ° C and calcined for 10 h at 650 ° C in an air atmosphere.
• a colorless powder (101.3 g) was obtained.
• the powder had a boron content of 1.3% by weight, calculated as elemental boron, a titanium content of 1.3% by weight, calculated as elemental titanium, and a silicon content of 40% by weight, calculated as elemental silicon, on.
• the total content of hydrocarbons was 0.1% by weight.
• the water absorption determined according to Reference Example 3 was 13.7% by weight.
• the 11 B solid-state NMR spectrum of the zeolitic material is shown in FIG.
• the 29 Si solid-state NMR spectrum of the zeolitic material is shown in FIG.
• the FT-IR spectrum of the zeolitic material is shown in FIG.
• the X-ray diffraction spectrum of the zeolitic Material is shown in FIG.
• the X-ray diffraction spectrum of the zeolitic material also has the following characteristics:
• Example 2 Preparation of a Pd / C catalyst A solution containing Pd was prepared as follows: 15.80 g of Pd (NO 3 ) 2 solution having a Pd content of 11% by weight was added to demineralized water to give 1: 1 wt Total volume of 136 mL filled. 172 g of SupersorbonO activated carbon (particle size 0.7-1, 0 mm) were soaked in this solution; It was then dried for 16 h at 80 ° C in a drying oven. Subsequently, the catalyst was calcined for 4 h at 400 ° C in a rotary kiln under N 2 stream. The 1 wt% Pd / C catalyst was then doped with KOH.
• the resulting mixture contained essentially dihydroxycyclohexane.
• the following distillation conditions were used: external temperature: 100 to 102 ° C; Bottom temperature: 90 to 92 ° C (column heating: 90 ° C); Head temperature: 81 to 82 ° C; Top pressure: 20.0 mbar.
• a reaction column was charged with 13 mL (5 g) of catalyst (1 wt% Pd on charcoal, prepared according to Example 2 and prewashed with 5 wt% aqueous KOH solution) and packed with quartz rings (30 mL below the catalyst bed, 30 ml over the catalyst bed).
• the catalyst was activated by purging with a gas mixture of N 2 / H 2 (95: 5) at 400 ° C for 15 min. Thereafter, it was rinsed with H 2 for a further 15 min. After purging with N 2 , the reactor temperature was set at 300 ° C (the reactor temperature is the temperature of the fixed catalyst bed, the measurement of which temperature is via a thermocouple placed radially centered and centered in the fixed catalyst bed).
• Example 3 An additional evaporator for pre-evaporation of the 2-methoxycyclohexanol feed stream from Example 3 at 275 ° C was connected.
• the carrier gas used was N 2 (20 L / h) and H 2 (2.5 L / h).
• the 2-methoxycyclohexanol obtained in Example 3 as a feed stream (25% by weight aqueous solution) was added to the reactor system (pre-evaporator + reactor) at a flow rate of 6 g / h. After 100 hours of continuous operation, a 2-phase product mixture was obtained.
• the mixture was then extracted with toluene (3 x 300 mL) to remove and recycle unreacted guaiacol.
• the resulting aqueous phase was further acidified with 97 to 99% by weight H 2 SO 4 (15.4 g, 0.15 mol) until the pH reached about 1.0.
• An aqueous solution of the mandelic acid derivative of the formula (III) was obtained.
• This crude solution of the mandelic acid derivative was heated together with toluene (160 mL) to a temperature of 90 ° C. Then, an aqueous 20% by weight FeCl 3 solution (282.4 g) was added over 30 minutes, whereby the red solution turned black. The mixture was then further stirred at 90 ° C for 2 h.
• FIG. 1 shows the 11 B solid-state NMR spectrum of the zeolite according to Example 1, measured according to Reference Example 1.
• the x-axis shows the 11 B chemical shift (in ppm) on the Y-axis.
• Ax is the intensity ( * 10 6 ).
• the scale markings on the X axis are, from left to right, at 40, 20, 0, -20.
• the scale markings on the Y axis are, from bottom to top, 0, 1, 2, 3, 4.
• FIG. 2 shows the 29 Si solid-state NMR spectrum of the zeolite according to Example 1, measured according to Reference Example 2.
• the X-axis shows the 29 Si chemical shift (in ppm), and the Y axis shows the intensity (FIG. * 10 6 ).
• the scale marks on the X-axis are, from left to right, at -90, -100, -110, -120, - 130.
• the scale line marks on the Y axis are, from bottom to top, at 0, 20, 40, 60, 80, 100.
• Example 3 shows the FT-IR spectrum of the zeolite according to Example 1, measured according to Reference Example 4.
• the X-axis shows the wavelength (in cm -1 ) on the Y axis.
• the scale line markings on the X axis are, from left to right, 4000, 3500, 3000, 2500, 2000, 1500.
• the scale line markings on the Y axis are, from bottom to top, at 0.00, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.1 1, 0.12, 0 , 13, 0.14, 0.15, 0, 16, 0.17, 0.18,
• the wavenumbers given in the individual peaks are in cm -1 , from left to right, 3748,
• Example 4 shows the X-ray diffraction pattern (copper K-alpha radiation) of the zeolite according to Example 1, measured according to Reference Example 5.
• the X-axis shows the degree values (2 theta), the y-axis shows the intensity (Lin (counts )).
• the X-axis scale markings are, from left to right, 2, 10, 20, 30, 40, 50, 60, and 70.
• the scale line marks on the Y axis are included, from bottom to top 0 and 3557 Quoted literature
• Titanium-substituted zeolite beta an efficient catalyst in the oxy-functionalization of cyclic alkenes using hydrogen peroxide in organic solvents, New J. Chem., 1998, pp. 797-799

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