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WO2012025548A1 - Procédé pour la préparation d'alcénones - Google Patents

Procédé pour la préparation d'alcénones Download PDF

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Publication number
WO2012025548A1
WO2012025548A1 PCT/EP2011/064503 EP2011064503W WO2012025548A1 WO 2012025548 A1 WO2012025548 A1 WO 2012025548A1 EP 2011064503 W EP2011064503 W EP 2011064503W WO 2012025548 A1 WO2012025548 A1 WO 2012025548A1
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Prior art keywords
reaction
microreactor
process according
carboxylic acid
alkenone
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Max Josef Braun
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Solvay SA
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Solvay SA
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    • 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
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
    • 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
    • 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
    • B01J19/18—Stationary reactors having moving elements inside
    • 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
    • C07C45/41—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenolysis or reduction of carboxylic groups or functional derivatives thereof
    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
    • 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
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/00033—Continuous processes
    • 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
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/0004—Processes in series
    • 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
    • B01J2219/00851—Additional features
    • B01J2219/00858—Aspects relating to the size of the reactor
    • B01J2219/0086—Dimensions of the flow channels
    • 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
    • B01J2219/0095—Control aspects
    • B01J2219/00984—Residence time

Definitions

  • the present invention relates to a process for preparing alkenones, in particular alkenone ethers.
  • Halogenated alkenone ethers such as 4-ethoxy- 1, 1, 1 -trifluoro-3 -butenone
  • ETFBO are building blocks in chemical synthesis, as disclosed, for example, in U.S. Pat. No. 5,708,175. They may be prepared by reacting an acid chloride with a vinyl ether in the presence of a base, as described in the aforementioned U.S. patent.
  • WO 03/066558 discloses the production of alkenones from vinyl ethers and acid halides or acid anhydrides in the presence of onium salts.
  • trifluoroacetic anhydride is added to ethyl vinyl ether
  • both addition of ethyl vinyl ether to a reaction medium containing trifluoroacetic anhydride and addition of trifluoroacetic anhydride to a reaction medium containing ethyl vinyl ether are described.
  • WO 2004/108647 discloses the production of alkenones comprising addition of carboxylic acid halides to vinyl ethers.
  • alkenones comprising addition of carboxylic acid halides to vinyl ethers.
  • trifluoroacetyl chloride is added to ethyl vinyl ether.
  • WO 2010/000871 discloses the manufacture of alkenones in a
  • alkenone ethers can be prepared by the known processes, these processes are still not optimal with regard to selectivity and yield of the reaction.
  • the invention relates to a process for preparing an alkenone, which comprises the following reaction steps: (a) reacting a carboxylic acid halide with a vinyl ether to form a halogenated precursor of the alkenone and (b) eliminating hydrogen halide from said precursor to form the alkenone, wherein reaction step (a) is at least partially conducted in a microreactor.
  • Ri is preferably a fluorinated C1-C4 alkyl group. Ri more preferably represents methyl, ethyl, n-propyl, isopropyl or methyl, ethyl, n-propyl or isopropyl substituted by at least one fluorine atom. It is especially preferred if Ri represents methyl, ethyl or methyl or ethyl substituted by at least one fluorine atom. CF 3 , CF 2 H, CF 2 C1, C 2 F 5 , C 3 F 7 are particularly preferred as Ri . CF 3 , CF 2 C1 and CF 2 H are more particularly preferred as Ri .
  • R 2 can be selected for example from aryl, for example, phenyl, C1-C4 alkyl groups and/or phenyl substituted by halogen atoms.
  • R 2 is preferably a C1-C4 alkyl group. More preferably, R 2 represents a linear or branched C1-C4 alkyl group, and particularly preferably R 2 represents methyl, ethyl, n-propyl or isopropyl, most preferably a methyl or an ethyl group.
  • X is preferably selected from fluorine and chlorine, more preferably X is chlorine.
  • the carboxylic acid halide is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-a first particular embodiment, the carboxylic acid halide is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoeth
  • the carboxylic acid halide is chlorodifluoroacetyl chloride.
  • the carboxylic acid halide is
  • the carboxylic acid halide is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-a forth particular embodiment
  • the carboxylic acid halide is
  • step (a) comprises reacting a carboxylic acid halide with a vinyl ether by introducing vinyl ether into a reaction medium containing the carboxylic acid halide to form the halogenated precursor of the alkenone.
  • the reaction medium contains the carboxylic acid halide, optionally an additional solvent and optionally the alkenone or the halogenated precursor to be produced.
  • step (a) comprises reacting a carboxylic acid halide with a vinyl ether by introducing the carboxylic acid halide into a reaction medium containing the vinyl ether to form the halogenated precursor of the alkenone.
  • the reaction medium contains the vinyl ether, optionally an additional solvent and optionally the alkenone or the halogenated precursor to be produced.
  • the reaction steps (a) or (b) can be carried out in the presence of a base.
  • the base to be used may, for example, be a nitrogen-containing heterocyclic compound such as pyridine, quinoline or picoline; or a tertiary base such as triethylamine, dimethylaniline, diethylaniline or 4-dimethylaminopyridine.
  • pyridine, triethylamine, dimethylaniline, diethylaniline or 4- dimethylaminopyridine is preferred.
  • pyridine is particularly preferred.
  • These bases may be used alone or in combination as a mixture. If appropriate, the base is used usually in an amount of from 1.0 to 3.0 equivalents, preferably from 1.05 to 1.5 equivalents, per mol carboxylic acid halide.
  • the reaction steps (a) or (b) can be carried out in the presence of an additional solvent.
  • additional solvent is understood to denote a solvent different from the reactants and the products of said reaction.
  • the solvent to be used can, for example, be an aromatic hydrocarbon such as benzene, toluene or xylene, an aliphatic hydrocarbon such as pentane or hexane; a halogenated hydrocarbon such as a chlorinated hydrocarbon selected in particular from methylene chloride, chloroform or ethylene dichloride or a fluorinated hydrocarbon selected in particular from 1,1, 1,3,3-pentafluoropropane or, preferably 1,1, 1,3,3-pentafluorobutane ; or an ether such as diethyl ether, dibutyl ether or tetrahydrofuran.
  • an aromatic hydrocarbon is preferred. Particularly preferred among them, is benzene or toluene.
  • these solvents can be used alone or in combination as a mixture. If appropriate, the solvent is used usually in an amount of from 1 to 35 parts by weight, preferably from 3 to 16 parts by weight, per part by weight of the reaction medium. Preferably, no additional solvent is present in the reaction medium.
  • organic products of the reactions of step (a) and (b) in particular the halogenated precursor of the alkenone and, preferably, the alkenone to be produced can be used as solvents for the reaction steps (a) and/or (b).
  • reaction step (a) the reaction of the carboxylic acid halide with the vinyl ether in reaction step (a) is carried out in a reaction medium comprising the alkenone to be produced, in particular ETFBO.
  • the alkenone is generally used in an amount of from 10 to 99 % by weight, preferably from 10 to 60 % by weight, more preferably from 15 to 35 % by weight relative to the total weight of the reaction medium.
  • the reaction medium for the reaction of the carboxylic acid halide with the vinyl ether comprises a halogenated precursor of the alkenone to be produced, in particular CETFBO ( 1,1, 1 -trifluoro-4-chloro-4- ethoxybutan-2-one).
  • the halogenated precursor is generally used in an amount of from 10 to 99 % by weight, preferably from 10 to 60 % by weight, more preferably from 15 to 35 % by weight of the halogenated precursor to the total weight of the reaction medium.
  • the presence of the halogenated precursor of alkenone to be produced is preferred when the reaction medium comprises carboxylic acid halide.
  • step (a) comprises reacting a carboxylic acid halide with a vinyl ether by introducing the carboxylic acid halide into the reaction medium containing the vinyl ether and the alkenone to be produced and/or the halogenated precursor to be produced.
  • the alkenone preferably comprises alkenone from an earlier batch of alkenone produced according to the processes as described herein.
  • the carboxylic acid halide to be introduced into the reaction medium can be dissolved in the alkenone to be produced and/or the halogenated precursor to be produced before introduction into the reaction medium.
  • the reaction of the carboxylic acid halide with the vinyl ether in reaction step (a) is carried out by adding the vinyl ether to a reaction medium which contains carboxylic acid halide
  • the content of the carboxylic acid halide is typically at least 20 % by weight relative to the total weight of the reaction medium. Preferably this content is at least 50 % weight.
  • the reaction medium may consist essentially of carboxylic acid halide. However, preferably the reaction medium generally contains less than 100 % by weight of carboxylic acid halide, for example less than about 99 % by weight, relative to the total weight of the reaction medium.
  • the reaction medium when the vinyl ether is added to the reaction medium which comprises carboxylic acid halide, the reaction medium contains at least 1 % by weight of carboxylic acid halide relative to the total weight of the reaction medium. Preferably this content is at least 5 % weight. In this embodiment, the reaction medium generally contains less than about 20 % by weight of carboxylic acid halide relative to the total weight of the reaction medium. Preferably this content is less than 10 % weight. Preferably, the reaction medium contains 5 to 10 % by weight of carboxylic acid halide relative to the total weight of the reaction medium.
  • step (a) as described above which step corresponds to the preparation of a halogenated precursor of the alkenone, can advantageously be carried out in a microreactor, at least partially.
  • Microreactors are known in the art (cf. e.g. WO 2007/042313 A2, US
  • Microreactors as used herein is understood in the broadest technical meaningful sense. In the art often "micromixer” and “microreactor” are used as synonyms. In some cases, however, a microreactor which mixes a plurality of fluids together is called a "micromixer” and a microreactor which causes a chemical reaction during the mixing of a plurality of fluids is called a "microreactor”.
  • the microreactor as used herein is a device comprising "micromixers", “microreactors” and combinations of these as used in the art.
  • microreactor is a device which comprises components, typically channels or flow ducts, having characteristic/determining geometric dimensions of 1 ⁇ to 2000 ⁇ , and in particular preferable from 10 ⁇ to 1000 ⁇ .
  • a microreactor is typically provided with a reaction channel which leads to a plurality of fine reaction channels or flow ducts. The equivalent diameter obtained in the section of the fine reaction channel is, converted to a circle, several micrometers to several hundreds of micrometers.
  • microreactor as used herein includes at least one micromixer, which is preferably used in combination with a further microreactor.
  • microreactor can be a device, which is referred to in the art as “minireactor”, “micro heat exchanger”, “minimixer” or “micromixer”. Examples of these are microreactors, micro heat exchangers, and T- and Y-mixers, as available by a large number of companies (e.g. Ehrfeld Mikrotechnik BTS
  • microreactor comprises a known static micromixer, more preferably a multi-lamination mixer, split and recombine mixers, or else mixers with a cross-sectional constriction.
  • the static micromixers are flowed through continuously.
  • known static micromixers are stack mixers as described in DE 202 06 371 Ul, slotted plate mixers, as described in WO 2004/052518 A2, or else comb mixers, as described e.g. in DE 202 09 009 Ul, as available by, for example, Ehrfeld Mikrotechnik BTS GmbH.
  • multi-lamination mixers in which the two fluid streams to be mixed are fanned out into a multitude of thin lamellae or films, and these lamellae are then merged with one another in alternation, such that the diffusion and secondary flows result in rapid mixing.
  • V-type mixers As alternative micromixers, V-type mixers, as available by
  • the microreactors comprise channels with channel widths of less than 1000 ⁇ , preferably less than 500 ⁇ , more preferably less than 200 ⁇ , in particular less than 100 ⁇ .
  • the microreactor applied in the process according to the present invention comprises a micromixer, and more preferably comprises a combination of a micromixer with a further microreactor, most preferably a sandwich type microreactor.
  • the further microreactor used is a micro heat exchanger or a microreactor having an integrated static mixing function, in which the reaction can be carried out under defined flow conditions, such as low axial and good radial mixing.
  • a sandwich type reactor from Ehrfeld Mikrotechnik BTS GmbH is used, more preferably in combination with a micromixer, in particular a cascade mixer. The temperature of the
  • microreactors as used herein can preferably be controlled by use of a temperature control fluid circulating through and/or around the microreactor.
  • microreactor comprises a static mixer, preferably a
  • microstructured static mixer in particular the mixers as specified above, most preferably in combination with a further microreactor, in particular a sandwich type microreactor.
  • microstructured heat exchangers are used as microreactors.
  • These known heat exchangers include micro-heat exchangers which consist of stacked thin plates provided with microchannels and welded to one another.
  • Microstructure heat exchangers are, e.g. cross-current or counter-current plate heat exchangers as described in DE 37 09 278 Al .
  • Such heat exchangers are available from Ehrfeld Mikrotechnik BTS GmbH.
  • the microreactor applied in the process according to the present invention is a combination of a micromixer as described above and a microstructured heat exchanger.
  • the microreactor in particular the static micromixer is flowed through continuously.
  • the reaction mixture can advantageously be kept at the optimal reaction temperature of around 0°C to 40°C, preferably from 10°C to 30°C, more preferably about 25°C or about 20°C.
  • the high heat transfer performance of the microreactors, in particular of the microstructured heat exchangers thereby guarantees that the temperature can be kept in the optimal range, in particular also during the first stages of the reaction, where typically the most reaction heat (enthalpy) is generated.
  • the small volumes of the reaction mixture allow exact temperature control and thereby prevent an undesired rise in the temperature which typically leads to side reactions and loss in selectivity.
  • the efficiency of the process is enhanced, since, owing to the very high exchange area per unit volume, it is possible to work with more highly concentrated reaction and work-up mixtures.
  • the intensive mixing of the phases additionally leads to acceleration of the preparation and work-up reaction, and to improved reaction conversion and increase in yield and selectivity of the reaction.
  • the process for preparing an alkenone according to the present invention is at least partially conducted in a microreactor.
  • Partially as used herein means that the reaction, e.g. mixing the carboxylic acid halide with the vinyl ether is not conducted in the microreactor until completion, but that the reaction medium discharged from the microreactor contains significant amounts of the carboxylic acid halide to be reacted and/or the vinyl ether to be reacted, respectively.
  • the reaction is substantially completed in a continuously stirred tank reactor (CSTR), which follows the microreactor.
  • CSTR continuously stirred tank reactor
  • a bubble column reactor or a similar reactor can also be used.
  • the invention will be explained with respect to a CSTR reactor, however, all the following explanations are also valid for a bubble column reactor.
  • the process, in particular step (a), is carried out in continuous mode.
  • the starting ingredients are preferably continuously fed into the microreactor, optionally followed by feeding the product obtained from the microreactor into a continuously stirred tank reactor.
  • the content of the halogenated precursor of the alkenone in the liquid reaction medium is preferably kept in a range from 50 to 99 %, preferably in a range from 60 to 99 %, more preferably in a range from 75 to 99 % by weight of halogenated precursor relative to the total weight of the reaction medium.
  • CSTR continuously stirred tank reactor
  • the carboxylic acid halide is reacted with the vinyl ether in step (a) such that the residence time of the reaction mixture in the microreactor is not sufficient for a substantially complete reaction.
  • the residence time in the microreactor is selected such that about 90% or less, more preferably about 70% or less, in particular about 50 % or less of the starting ingredient has reacted.
  • the starting ingredient which can react completely is the carboxylic acid halide or the vinyl ether, whichever of the two is present in a lower molarity in the reaction mixture. If the molar ratio of carboxylic acid halide and vinyl ether is about 1, preferably the vinyl ether is the relevant starting ingredient.
  • the residence time in the microreactor is preferably less than 80%, more preferably less than 60%, in particular less than 50% of the residence time necessary to achieve substantially completion of the reaction at the respective reaction conditions.
  • the residence time in the microreactor is preferably less than 80 minutes, more preferably less than 40 minutes, in particular less than 20 minutes.
  • the reaction of the carboxylic acid halide with the vinyl ether in the process according to the present application is preferably continued, more preferably substantially completed in a continuously stirred tank reactor (CSTR), which reactor most preferably directly follows the microreactor.
  • CSTR continuously stirred tank reactor
  • this reaction is carried out continuously.
  • the carboxylic acid halide and vinyl ether are mixed and partially reacted in a microreactor, followed by substantial completion of the reaction in a continuously stirred tank reactor.
  • Substantially complete typically denotes an optional content of 1% by weight or less of the starting ingredient, more preferred 0.5% by weight or less, more preferred 0, 1 % by weight or less of starting ingredient relative to the weight of the end product.
  • Reaction step (a) of the process of the present invention can also comprise completion of the reaction step in a plug-flow reactor.
  • the reaction mixture, which has been at least partially brought to reaction in the microreactor can be further reacted in the microreactor or a stirred tank reactor and then substantially completed (or completed) in a plug-flow reactor.
  • substantially completed (or completed) in a plug-flow reactor e.g. the last 5%, preferably the last 2% or the last 1% of the reaction of reaction step (a) is carried out in a plug-flow reactor.
  • the CSTR reactor is usually in the turbulent state while the plug-flow reactor can be in the turbulent state or in the laminar-flow state.
  • microreactor optionally followed by an CSTR and optionally followed by a plug-flow reactor is advantageous as the advantages of the specific reactors are combined.
  • the microreactor is particularly advantageous as it typically provides excellent heat exchange, and thereby is able to control the reaction heat (enthalpy), which is set free mostly at the beginning of the reaction. Therefore, already at the stage of the beginning of the reaction heating of the reaction mixture above the optimal temperature range of e.g. ⁇ 20°C is avoided, whereby yield and selectivity of the reaction is increased.
  • the completion of the reaction can then be carried out in a continuously stirred tank reactor and/or a plug-flow reactor.
  • step (a) or (b) is carried out in the substantial or complete absence of a base, especially when a carboxylic acid chloride as described herein before is used.
  • step (a) or (b) is carried out in the substantial or complete absence of additional solvent.
  • reaction of step (a) or (b) is preferably carried out in the substantial or complete absence of base and of additional solvent, as described here before.
  • Substantial absence typically denotes an optional content of 1 % by weight or less, more particularly of 0.5 % by weight or less of base and/or solvent relative to the total weight of the reaction mixture.
  • the process according to the invention allows for particularly efficient isolation of, if desired, the halogenated precursor of the alkenone and in particular the desired alkenone, because the reaction proceeds selectively and separation is facilitated by the substantial absence of components different from the starting material and the products of the reaction.
  • the molar ratio of the carboxylic acid halide to the vinyl ether preferably is from 0.8 to 1.2, and particularly preferably from 0.8: 1 to about 1. Most preferably, the molar ratio is about 1.
  • the vinyl ether is preferably introduced into the reaction medium at a rate of from 0.01 to 2 mol/hour/mol of carboxylic acid halide. More preferably this rate is from 0.5 to 1.5 mol/hour/mol of carboxylic acid halide. A rate of about 1 mol/hour/mol of carboxylic acid halide has provided good results.
  • the reaction medium comprises vinyl ether
  • the concentration of the vinyl ether in the reaction medium is equal to or more than 80 % by weight relative to the total weight of the liquid reaction medium. More preferably, this concentration is equal to or more than 90 % by weight relative to the total weight of the reaction medium, and may be at least 95 % by weight relative to the total weight of the reaction medium.
  • the process according to the present invention is generally carried out at a temperature from 0°C to 40°C, preferably from 10°C to 30°C, more preferably at about 25°C or about 20°C.
  • the vinyl ether, the carboxylic acid halide and any optional solvents are mixed in step (a) by use of a micromixer, preferably followed by introduction of the mixture into a further microreactor.
  • step (a) by carrying out step (a) at least partially in a microreactor, hot spots can be substantially avoided in said reaction medium, thereby improving the yield and purity of the halogenated precursor of the alkenone and of the alkenone obtained from the precursor.
  • the term “hot spot” denotes in particular a zone of the reaction medium having a substantially higher temperature than the target temperature at which the reaction should be carried out. "Substantially higher temperature” is understood a temperature which is at least 5°C, or at least 10°C higher than the target temperature of the reaction medium.
  • the reaction step (a) is preferably partially, more preferably completely, carried out in a microreactor, which preferably comprises at least one micromixer.
  • a microreactor which preferably comprises at least one micromixer.
  • the carboxylic acid halide, the vinyl ether and the optional solvent are preferably fed into a micromixer.
  • the micromixer is preferably a known static micromixer.
  • the mixture obtained from the micromixer is then fed into a further microreactor, e.g. a microstructured heat exchanger and/or a sandwich type microreactor.
  • a further microreactor e.g. a microstructured heat exchanger and/or a sandwich type microreactor.
  • the mixture is subsequently passed through an arrangement of microstructured heat exchangers with a given residence time.
  • the arrangement is preferably configured such that the temperature profile in the flowing reaction mixture along the flow direction is adjustable by application of one or a sequence of heat exchangers or a sequence of further microreactors.
  • the static micromixer is flowed through continuously, the obtained mixture is brought to a suitable temperature by means of one or more heat exchangers, and then the reaction mixture is optionally fed into one or more further microreactors, and optionally the reaction mixture is then passed to the CSTR and/or a plug-flow reactor according to the preferred embodiments as described above.
  • the turbulent state of the CSTR can be achieved, for example, by an operation selected from stirring, passing the reaction medium through a flow resistance or mixing the reaction medium through introduction of gas bubbles such as an inert gas (in a bubble column reactor).
  • the stirring in the reaction medium may be realized by means of internal stirring such as a turbine or an agitator, or by means of a recirculation pipe exterior to the reactor.
  • Typical examples of a flow resistance are for example shaped bodies which can be placed in a reactor such as glass rings and Raschig rings.
  • Particular embodiments of CSTR as applied in the various embodiments according to the present invention include reactors which consist of one or more cylindrical or spherical tanks wherein the turbulent state of the liquid reaction medium is created by any of the means described above.
  • Particular embodiments of the plug flow reactor are in the form of a cylindrical tube through which the feed enters at one end and exits at the other end.
  • the process according to the invention and the particular embodiments thereof generally comprises carrying out the reaction of step (a) at a first temperature and carrying out step (b) at a second temperature higher than the first temperature.
  • the first temperature is generally less than 50°C, often less than 40°C, preferably 30°C or less. In one aspect, the temperature is preferably about -25°C or less.
  • the first temperature is generally at least -50°C, often -40°C or more, preferably -30°C or more. As the use of a microreactor already gives excellent yield and selectivity at room temperature it is preferred that the first temperature is in the range of about 10°C to about 50°C, more preferably about 20°C to about 30°C.
  • the second temperature is generally at least 50°C, often 60°C or more, preferably 70°C or more.
  • the second temperature is generally less than 150°C, often less than 100°C, preferably about 80°C or less.
  • the process according to the invention and the particular embodiments thereof generally comprises carrying out the reaction of step (a) at a first pressure and carrying out step (b) at a second pressure lower than the first pressure.
  • the first pressure is generally in the range of about 1 bar abs to about 100 bar abs.
  • the first pressure is preferably chosen to maintain the reaction medium and the reactands in the liquid state.
  • the first pressure is
  • the first pressure is advantageously a pressure of about 2 bar abs or more, more preferably about 5 bar abs to about 10 bar abs or more, in particular at a reaction temperature of from 20 to 30°C.
  • the second pressure is preferably chosen to allow for fractional distillation at least of the alkenone from the reaction medium obtained in step (a).
  • a typical second pressure is from 1 to about 10 "3 bar abs.
  • step (a) is carried out in a first reaction zone and step (b) is carried out in a second reaction zone different from the first reaction zone.
  • the first reaction zone is often a microreactor, optionally followed by a continuously stirred tank reactor and/or a plug-flow reactor.
  • the second reaction zone can be, for example, a distillation column.
  • the process according to the invention further comprises separating the alkenone produced in step (b) from hydrogen halide, unreacted carboxylic acid halide and unreacted halogenated precursor (and some traces of polymeric material) and optionally recycling carboxylic acid halide to step (a) and halogenated precursor to step (b).
  • a distillation in particular a fractional distillation, is preferred as separation technique to separate the alkenone, in particular from the reaction mixture of step (b).
  • thermolysis treatment selected from a flash thermolysis, a vacuum thermolysis and a thermolysis under stripping with an inert gas.
  • flash thermolysis refers to a process wherein the liquid reaction medium is heated up in a short time. Typical heating times for flash thermolysis are less than 1 hour, in particular less than 30 min, preferably about 15 minutes. Generally, the heating time is greater than Is, often greater than 15s.
  • the flash thermolysis is conducted at a temperature ranging from -20° C to 140° C and a period of time ranging from 30 seconds to 1 hour, preferably at a temperature ranging from 0° C to 130° C and a period of time ranging from 30 seconds to 30 min, more preferably at a temperature ranging from 20° C to 120° C and a period of time ranging from 30 seconds to 20 min.
  • thermolysis or flash thermolysis can be optionally carried out under stripping with an inert gas stream such as nitrogen gas, argon gas.
  • the term "stripping" denotes in particular a physical separation process where one or more components, in particular HC1, are removed from the liquid reaction medium by a gas stream.
  • the liquid and gas streams can have concurrent or countercurrent flow directions.
  • the stripping is advantageously carried out with a nitrogen stream.
  • the process according to this embodiment generally comprises carrying out the thermolysis at a temperature of -20° C to 140° C, preferably from 60 to 130°C, for example at about 80 °C or about 120 °C.
  • thermolysis or flash thermolysis may be carried out under vacuum.
  • the vacuum is preferably from 100 to 600 mbar.
  • the elimination of hydrogen halide is carried out simultaneously during the formation of the halogenated precursor of the alkenone, for example, in the presence of an acid scavenger and/or by thermally inducing the elimination of hydrogen halide.
  • the acid scavenger to be used may, for example, be a nitrogen- containing heterocyclic compound such as pyridine, quinoline or picoline; or a tertiary base such as thiethylamine, dimethylaniline, diethylaniline or 4- dimethylaminopyridine.
  • pyridine, triethylamine, dimethylaniline, diethylaniline or 4-dimethylaminopyridine is preferred.
  • pyridine is particularly preferred.
  • the acid scavenger is used in an amount of about 1 equivalent or less, preferably about 0.8 equivalents or less, in particular about 0.5 to about 0.8 equivalents per mol carboxylic acid halide.
  • an additional solvent may be present during the elimination of hydrogen halide.
  • additional solvent has the same meaning as defined above.
  • chlorotrifluoroalkoxybutanone from alkyl-vinylether and trifluoroacetic acid halide, in particular from trifluoroacetyl chloride and ethyl vinyl ether and subsequent elimination to form trifluoroalkoxybutenone, in particular ETFBO (4-ethoxy-l, 1, l-trifluoro-3-butenone).
  • chlorodifluoroalkoxybutanone from alkyl-vinylether and difluoroacetic acid halide, in particular from difluoroacetyl chloride and ethyl vinyl ether and subsequent elimination to form difluoroalkoxybutenone, in particular EDFBO (4-ethoxy- 1 , 1 -difluoro-3 -butenone).
  • the present invention further relates to a reactor for conducting the processes as described above comprising at least one microreactor, preferably the microreactors as defined above, in particular a micromixer and/or a sandwich- type microreactor, and a stirred tank reactor, preferably a CSTR and preferably a plug-flow reactor.
  • the microreactor and the stirred tank reactor preferably a CSTR (and optionally the plug-flow reactor) are connected to allow the passage of the fluid, i.e. the liquid reaction medium from the microreactor into the stirred tank reactor, preferably the CSTR as described above (and if required furtheron into the plug-flow reactor).
  • the microreactor and the stirred tank reactor are directly connected such that no intermediate device is arranged between the microreactor and the stirred tank reactor, such that the liquid reaction medium discharged from the microreactor is directly charged into the stirred tank reactor.
  • TFAC trifluoroacetylchloride
  • EVE ethyl vinyl ether
  • CETFBO 4-Chloro-4-Ethoxy-l, l, l-trifluoro-3-butan-2-one
  • ETFBO is Ethoxy-l, l, l-trifluoro-3-buten-2-one
  • DETFBO 4,4-Diethoxy- 1,1, 1 trifluoro-3-butan-2-one.
  • TFAC Gaseous trifluoracetylchlorid
  • ETFBO ETFBO
  • the feeding rate of the TFAC was controlled via a rotameter and the feeding rate of EVE, or the mixture with of EVE with ETFBO, respectively, was controlled via a dosing pump or a HPLC-pump.
  • the feeding rate was adjusted to obtain the residence time as indicated in the tables.
  • the mixing of the gaseous/liquid phase was achieved in the micromixer (a split and recombine micromixer), the temperature of which can be controlled. After passing the micromixer the reaction mixture was fed into the sandwich type microreactor, which can be controlled in temperature, in order to provide the desired residence time.
  • ONLINE-NIR Thermo Fischer device

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention porte sur un procédé pour la préparation d'alcénones, en particulier d'éthers d'alcénones, par la réaction d'un halogénure d'acide carboxylique avec un éther de vinyle et l'élimination d'halogénure d'hydrogène à partir dudit précurseur pour former l'alcénone.
PCT/EP2011/064503 2010-08-27 2011-08-24 Procédé pour la préparation d'alcénones Ceased WO2012025548A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9193656B2 (en) 2011-12-22 2015-11-24 Solvay Sa Process for the manufacture of halogenated precursors of alkenones and of alkenones
CN112979443A (zh) * 2019-12-13 2021-06-18 浙江蓝天环保高科技股份有限公司 一种三氟甲基丁烯酮类衍生物的连续制备方法

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Publication number Priority date Publication date Assignee Title
US9193656B2 (en) 2011-12-22 2015-11-24 Solvay Sa Process for the manufacture of halogenated precursors of alkenones and of alkenones
CN112979443A (zh) * 2019-12-13 2021-06-18 浙江蓝天环保高科技股份有限公司 一种三氟甲基丁烯酮类衍生物的连续制备方法

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