Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
  • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
  • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
  • C07C2/66—Catalytic processes
  • C07C2/70—Catalytic processes with acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00781—Aspects relating to microreactors
  • B01J2219/00819—Materials of construction
  • B01J2219/00835—Comprising catalytically active material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00781—Aspects relating to microreactors
  • B01J2219/00873—Heat exchange
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00781—Aspects relating to microreactors
  • B01J2219/00889—Mixing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00781—Aspects relating to microreactors
  • B01J2219/00905—Separation
  • B01J2219/00916—Separation by chromatography
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00781—Aspects relating to microreactors
  • B01J2219/0095—Control aspects

Definitions

• the present invention relates to processes for Fhedel-Crafts alkylation of organic compounds and alkylation microreactors for carrying out these processes.
• Another object was to provide an apparatus for performing this method.
• This object is achieved according to the invention by providing new processes for Friedel-Crafts alkylation of organic compounds in which the organic compound in liquid or dissolved form in the presence of a catalyst in liquid or dissolved form with an alkylating reagent in liquid or dissolved form in at least one microreactor is mixed, reacted during a residence time and the alkylated organic compound is isolated from the reaction mixture. -? -
• a microreactor in the sense of the invention is a reactor with a volume ⁇ 100 ⁇ l in which the liquids and / or solutions are mixed intimately at least once.
• the volume of the microreactor is preferably ⁇ 10 ⁇ l, particularly preferably ⁇ 1 ⁇ l.
• a microreactor is preferably produced from thin, interconnected silicon structures.
• the microreactor is preferably a miniaturized flow reactor, particularly preferably a static micromixer.
• the microreactor is very particularly preferably a static micromixer, as described in WO 96/30113, which is hereby introduced as a reference and is considered part of the disclosure.
• Such a microreactor has small channels in which liquids and / or chemical compounds present in solutions are preferably mixed with one another by the kinetic energy of the flowing liquids and / or solutions.
• the channels of the microreactor preferably have a diameter of 10 to 1000 ⁇ m, particularly preferably from 20 to 800 ⁇ m and very particularly preferably from 30 ⁇ m to 400 ⁇ m.
• the liquids and / or solutions are preferably pumped into the microreactor in such a way that they flow through them at a flow rate of 0.1 ⁇ l / min to 10 ml / min, particularly preferably 1 ⁇ l / min to 1 ml / min.
• the microreactor can preferably be tempered.
• the residence time in the sense of the invention is the time between the mixing of the organic compounds, catalysts and alkylation reagents or their solutions and the working up of this reaction solution for the analysis or isolation of the desired product (s).
• the required residence time in the processes according to the invention depends on various parameters, such as the reactivity of the organic compounds, catalysts and alkylation reagents used, the desired degree of alkylation or the temperature. It is possible for a person skilled in the art to adapt the dwell time to these parameters and thus to achieve a timely response.
• the residence time of the reaction solution in the microreactor if appropriate in the microreactor and the residence zone, is preferably ⁇ 3 hours, preferably ⁇ 1 hour.
• the microreactor is preferably connected via an outlet to at least one retention zone, preferably a capillary, particularly preferably a temperature-controlled capillary.
• the liquids and / or solutions are passed into this residence zone or capillary after they have been mixed in the microreactor in order to extend their residence time.
• the reaction mixture is likewise preferably passed through two or more microreactors connected in parallel or in series. The result of this is that the residence time is extended even at an increased flow rate and the components of the alkylation reaction used are converted almost completely to the desired alkylated organic compound (s).
• the number and the arrangement of the channels in one or more microreactor (s) are varied in such a way that the residence zone is lengthened, so that here too, with an increased flow rate, an almost complete conversion to the desired alkylated one or more organic compounds) is achieved.
• the residence time of the reaction solution in the system used can also be set by selecting the flow rate of the liquids and / or solutions used.
• the processes according to the invention can be carried out in a very wide temperature range, which is essentially due to the temperature resistance of the materials used for the construction of the microreactor, possibly the residence zone, and further constituents, such as, for example, connections and seals, and the physical properties of the solutions used and / or Liquids is limited.
• the processes according to the invention are preferably carried out at a temperature of from -90 to +150 to ° C, particularly preferably from -20 to +100 ° C, very particularly preferably from -10 to +80 ° C.
• the processes according to the invention can be carried out either continuously or batchwise. They are preferably carried out continuously.
• the course of the alkylation reaction in the processes according to the invention can be followed and, if necessary, regulated using the various analytical methods known to the person skilled in the art.
• the course of the reaction is preferably followed by chromatography, particularly preferably by gas chromatography, and, if appropriate, regulated.
• the alkylated organic compounds can also be isolated by the various methods known to the person skilled in the art.
• the alkylated product (s) is / are preferably isolated from the reaction mixture by extraction, preferably with an organic solvent or by precipitation, preferably with an organic solvent and / or water, particularly preferably with water.
• Aromatic or heteroaromatic compounds are preferably used as organic compounds. These aromatic or heteroaromatic compounds include both monocyclic and polycyclic compounds, as well as compounds which have a monocyclic and / or polycyclic, homo- or heteroaromatic basic structure or a partial structure, e.g. in the form of substituents.
• aromatic compounds are benzene, naphthalene, azulene, anthracene, phenanthrene, pyrene, fluorene, quinones such as ortho and para-benzoquinone, naphthoquinones, flouronones, anthrones, phenanthrones, anthraquinones and / or their derivatives, in particular their alkyl, derivatives used.
• Particularly preferred heteroaromatic compounds are oxygen-containing, heteroaromatic compounds and / or their derivatives, very particularly preferably furans, such as, for example, benzanellated furans, dibenzofurans, dibenzodioxanes, pyrylium cations and benzopyranones.
• nitrogen-containing, heteroaromatic compounds and / or their derivatives such as, for example, pyrroles, pyrazoles, imidazoles, triazoles, tetrazoles, pyridines, pyrazines, pyrimidines, pyridinium salts, triazines, tetrazines, pyridine-N-oxides, benzanellated pyrroles , such as indoles, carbazoles, benzimizazoles or benzotriazoles, phenanzine, quinolines, isoquinolines, cinnolines, quinazolines, quinoxalines, phenanthroline, bipyridyls and their higher homologues, acridines, acridones, and / or pyrene.
• pyrroles such as, for example, pyrroles, pyrazoles, imidazoles, triazoles, tetrazoles, pyridines, pyr
• Sulfur-containing, heteroaromatic compounds and / or their derivatives such as, for example, thiophenes, benzanellated thipophenes, in particular benzothiophenes or dibenzothiophenes, and also acenaphthylenes, thiazoles, isothiazoles, biphenylenes, purines, benzothiadiazoles, oxazoles and / or
• organometallic compounds whose organic partial structure can be alkylated by a Friedel-Crafts alkylation.
• organometallic compounds are metallocenes of metals in the fourth to eighth subgroup of the periodic table, very particularly preferably metallocenes of metals in the fourth to eighth subgroup of the periodic table with at least one cyclopentadienyl ligand in the processes according to the invention.
• alkylation reagents are olefins, particularly preferably ethene, propene, dodecene or linear olefins with a chain length of 20 to 30 carbon atoms, alkyl halides, particularly preferably methyl chloride, methyl iodide, ethyl chloride, isopropyl chloride, tert-butyl chloride, benzyl chloride or cyclohexyl chloride, alcohols, ethers, esters inorganic and organic acids, epoxides, aldehydes, ketones, thiols, dialkyl sulfates, alkyl p-tolyl sulfonates, trifluoromethanesulfonic acid or their esters, aliphatic diazo compounds and / or trialkyloxonium t
• the organic compounds, alkylation reagents and catalysts used are either themselves liquid or are in dissolved form. If these compounds are not themselves already in liquid form, they must therefore be used in a suitable one before carrying out the processes according to the invention
• Solvent are dissolved.
• Preferred solvents are halogenated hydrocarbons, particularly preferably dichloromethane, chloroform, 1, 2-dichloroethane or 1, 1, 2,2-tetrachloroethane, paraffins, particularly preferably hexane or ligroin, ether, particularly preferably diethyl ether, acid amides, particularly preferably N, N-dimethylformamide, nitriles, particularly preferably acetonitrile, carbon disulfide, nitroaliphatics, particularly preferably nitromethane, nitroaromatics, particularly preferably nitrobenzene or mixtures thereof.
• Ionic liquids which are liquid eutectics at room temperature are also preferably used as solvents.
• Particularly preferred ionic liquids are N-butyl-N-methylimidazolium tetrachloroaluminate, N-ethyl-N-methylimidazolium tetrachloroaluminate, N-ethyl-N-methylimidazolium tetrafluoroborate, N-alkylated pyridinium imidazolium salts, in particular their tetrafluoro or hexafluorobluoro or hexafluorobluorobluorobluoroborate or their tetrafluoro or hexafluoroborate or hexafluoroborate or especially their tetrafluoro or hexafluoroborate or hexafluorobluorobluoride or especially their tetrafluoro or hexafluoroborate or their te
• the molar ratio of organic compound to alkylation reagent used in the processes according to the invention depends on the one hand on the reactivity of the organic compounds, catalysts and alkylation reagents used and on the other hand on the desired degree of alkylation.
• the degree of alkylation itself depends on a number of other parameters, such as the concentration of the reagents used, e.g. Temperature, type of catalyst or residence time. It is possible for the person skilled in the art to adapt the various parameters to the respective alkylation reaction in such a way that the desired single or multiple alkylated product is obtained.
• the molar ratio of organic compound to alkylating reagent is preferably 1 to 10, preferably 1, 1 to 2 and particularly preferably 1, 2 to 1, 5 for the preparation of a mono-alkylated compound.
• All catalysts known to the person skilled in the art and suitable for Friedel-Crafts alkylations can be used as catalysts in the processes according to the invention.
• Lewis acids are preferably also used as catalysts, if appropriate also dissolved in ionic liquids, protonic acids, ionic liquids, organometallic catalysts and / or mixtures thereof.
• catalysts chloroacetic acid, trifluoroacetic sigklad, trifluoromethanesulfonic anhydride, dihalogenated phosphoric, sulfuric, hydrochloric, phosphoric, sulfonic acids, very particularly preferably alkyl sulfonic acids such as methanesulfonic acid or arylsulfonic acid, iron trihalides, tin tetrachloride, aluminum halides, alkylaluminum halides, boron trihalides, ionic liquids, which at Eutectics which are liquid at room temperature, such as, for example, N-butyl-N-methylimidazolium tetrachloroaluminate, N-ethyl-N-methylimidazolium tetrachloroaluminate, N-ethyl-N-methylimidazolium tetrafluoroborate or N-alkylated pyridinium imidazolium
• the amount of the catalyst used in the process according to the invention is preferably between 0.1 and 110 mol%, particularly preferably between 1 and 100 mol%, based on the amount of organic compound used.
• Another object of the invention is an alkylation microreactor for carrying out the process according to the invention.
• This alkylation micro-reactor has at least one mixing element and optionally a residence zone and its volume, without the volume of the residence zone, is preferably ⁇ 10 ⁇ l, particularly preferably ⁇ 1 ⁇ l.
• the alkylation microreactor is a static micromixer. In a further preferred embodiment of the alkylation microreactor, it has a residence zone which is a capillary which is connected to an outlet of the alkylation microreactor.
• the capillary is preferably a temperature-controllable capillary.
• the alkylation microreactor itself can likewise preferably be temperature-controlled.
• the risk to humans and the environment from chemicals being released is considerably reduced. Furthermore, the risk of explosion in the case of very strongly exothermic alkylation reactions is reduced, inter alia, by an improved mass and heat transport compared to conventional systems.
• An official approval according to the BlmschG (BGBI. I No. 71 of October 26, 1998 p. 3178) for the operation of systems for the implementation of the method according to the invention is therefore much easier to obtain.
• the processes according to the invention can be carried out continuously. As a result, they can be carried out more quickly and more cost-effectively than conventional methods, and it is possible to produce any amounts of the alkylated organic compounds without great expenditure on measurement and control.
• the course of the alkylation reaction can be regulated very quickly in the process according to the invention.
• the alkylation of organic compounds by the processes according to the invention also enables better control over the reaction time and reaction temperature than is possible in the conventional processes.
• the proportion of mono-alkali products can be increased compared to double and triple-alkali products.
• the temperature can be individually selected and kept constant in each volume element of the system. The alkylated organic products can thus be obtained in very good and reproducible yields.
• the total pressure loss across all 11 mixing stages was approx. 1000 Pa.
• the static micromixer was connected via an outlet and an Omnifit medium pressure HPLC connector component (Omnifit, Great Britain) to a Teflon capillary with an inner diameter of 0.25 mm and a length of 0.9 m.
• the static micromixer and the Teflon capillary were tempered in a double-jacket vessel filled with ethanol and thermostated at 0 ° C.
• a 20 ml polypropylene syringe was filled with a mixture of 4 ml (0.045 mol) benzene and 5 ml cyclohexene and a 1 ml glass syringe with a metal tip was filled with 1 ml (0.019 mol) 96% sulfuric acid.
• the contents of both syringes were then transferred to the static micromixer using a metering pump (Harvard Apparatus Inc., Pump 22, South Natick, Massachussets, USA). The flow rate was set at 10 ul / min.
• the mixed reaction solution was stirred into a beaker with 50 ml of water.
• the system of static micromixer and Teflon capillary was then rinsed first with 10 ml of water and then with 10 ml of dichloromethane.
• the combined liquid phases were then extracted three times with 20 ml dichloromethane each time.
• the combined organic extracts were dried over magnesium sulfate and the solvent was removed in vacuo. 8.3 g (corresponding to 58% of the theoretical yield) of a colorless oil were obtained, which crystallized out at a temperature of ⁇ 20 ° C. in the form of white crystals.
• the content of simply alkylated product (3) was 50 by a combined GC-MS analysis Area% of the chromatogram determined. In addition, 20 area% of cyclohexene and 5 area% of double-alkylated products were detected.

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• Chemical & Material Sciences (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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Citations (4)

• 1999
  • 1999-09-28 DE DE1999146368 patent/DE19946368A1/de not_active Withdrawn
• 2000
  • 2000-09-19 EP EP00969265A patent/EP1216216A1/de not_active Withdrawn
  • 2000-09-19 WO PCT/EP2000/009154 patent/WO2001023328A1/de not_active Application Discontinuation
  • 2000-09-19 JP JP2001526484A patent/JP2003510297A/ja active Pending
  • 2000-09-19 AU AU79047/00A patent/AU7904700A/en not_active Abandoned

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