EP2274270A1 - Kontinuierliches verfahren zur herstellung von amiden niederer aliphatischer carbonsäuren - Google Patents

Kontinuierliches verfahren zur herstellung von amiden niederer aliphatischer carbonsäuren

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Publication number
EP2274270A1
EP2274270A1 EP09727594A EP09727594A EP2274270A1 EP 2274270 A1 EP2274270 A1 EP 2274270A1 EP 09727594 A EP09727594 A EP 09727594A EP 09727594 A EP09727594 A EP 09727594A EP 2274270 A1 EP2274270 A1 EP 2274270A1
Authority
EP
European Patent Office
Prior art keywords
microwave
reaction
acid
atoms
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09727594A
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German (de)
English (en)
French (fr)
Inventor
Matthias Krull
Roman MORSCHHÄUSER
Michael Seebach
Hans Jürgen SCHOLZ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant International Ltd
Original Assignee
Clariant Finance BVI Ltd
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Publication date
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Publication of EP2274270A1 publication Critical patent/EP2274270A1/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • 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
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/122—Incoherent waves
    • B01J19/126—Microwaves
    • 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
    • B01J2219/02—Apparatus characterised by their chemically-resistant properties
    • B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
    • B01J2219/0254—Glass
    • 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
    • B01J2219/02—Apparatus characterised by their chemically-resistant properties
    • B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
    • B01J2219/0263—Ceramic
    • 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
    • B01J2219/02—Apparatus characterised by their chemically-resistant properties
    • B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
    • B01J2219/0277—Metal based
    • B01J2219/0281—Metal oxides
    • 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
    • B01J2219/02—Apparatus characterised by their chemically-resistant properties
    • B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
    • B01J2219/0295—Synthetic organic materials
    • 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
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0892—Materials to be treated involving 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
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/12—Processes employing electromagnetic waves
    • B01J2219/1203—Incoherent waves
    • B01J2219/1206—Microwaves
    • B01J2219/1209—Features relating to the reactor or vessel
    • B01J2219/1221—Features relating to the reactor or vessel the reactor per se
    • B01J2219/1224—Form of the reactor
    • B01J2219/1227—Reactors comprising tubes with open ends

Definitions

  • Amides of lower aliphatic carboxylic acids are very interesting as chemical raw materials.
  • various amides find use as intermediates for the manufacture of pharmaceuticals and agrochemicals.
  • the tertiary amides are aprotic, polar liquids with excellent dissolving power. They are used, inter alia, for the production of fibers and films as well as reaction medium. For example, they are used as solvents for polyacrylonitrile and other polymers, as paint stripper, extractant, catalyst and as crystallization aid.
  • GB-414 366 discloses a process for the preparation of substituted amides by thermal condensation.
  • higher-boiling carboxylic acids are reacted with gaseous secondary amines at temperatures of 200-250 ° C.
  • the crude products are purified by distillation or bleaching.
  • GB-719 792 discloses a process for the preparation of dimethylacylamides in which a C 2 -C 4 carboxylic acid and dimethylamine are reacted in excess dimethylacylamide such that the content of acid in the reaction mixture remains below the concentration of the azeotrope of acid and dimethylacylamide.
  • Reaction water which strongly attack or dissolve metallic reaction vessels at the required high reaction temperatures.
  • the metal contents thus introduced into the products are very undesirable because they not only affect the product properties in terms of their color but also catalyze decomposition reactions and thus reduce the yield.
  • the latter problem can be avoided in part by special reaction vessels made of highly corrosion-resistant materials or with corresponding coatings, which nevertheless requires long reaction times and thus leads to products impaired in their color.
  • unwanted side reactions are, for example, an oxidation of the amine, a thermal disproportionation of secondary amines to primary and tertiary amine and a decarboxylation of the carboxylic acid mentioned. All of these side reactions reduce the yield of the target product.
  • Vazquez-Tato Synlett 1993, 506, discloses the use of microwaves as a heat source for the preparation of amides from carboxylic acids and arylaliphatic amines via the ammonium salts. The syntheses were carried out on a mmol scale.
  • the inhomogeneity of the microwave field caused by localized overheating of the reaction mixture, caused by more or less uncontrolled reflections of the microwaves irradiated into the microwave oven on the walls thereof and the reaction mixture in the commonly used multimode microwaves causes problems in scale-up.
  • the microwave absorption coefficient of the reaction mixture which often changes during the reaction, presents difficulties with regard to a reliable and reproducible reaction.
  • Microwave absorption efficiency of the reaction product is low due to the microwave energy more or less homogeneously distributed in the applicator space in multimode microwave applicators and not focused on the coil.
  • a large increase in the radiated microwave power leads to unwanted plasma discharges.
  • the time-varying spatial inhomogeneities of the microwave field referred to as hot spots, make reliable and reproducible reaction on a large scale impossible.
  • single-mode or single-mode microwave applicators are known in which a single wave mode is used, which propagates in only one spatial direction and is focused by precisely dimensioned waveguides on the reaction vessel.
  • these devices allow higher local field strengths, so far due to the geometric requirements (eg, the intensity of the electric field at its wave crests is greatest and goes to zero at the nodes) so far on small reaction volumes ( ⁇ 50 ml) Laboratory scale limited.
  • a process has therefore been sought for the preparation of amides of lower carboxylic acids, in which carboxylic acid and amine can also be converted to the amide on an industrial scale under microwave irradiation.
  • the aim is to achieve as high as possible, that is to say quantitative, conversion rates.
  • the method should further enable a possible energy-saving production of carboxylic acid amides, that is, the microwave power used should be as quantitatively absorbed by the reaction mixture and thus offer the process a high energy efficiency. This should be incurred no or only minor amounts of by-products.
  • the amides should also have the lowest possible metal content and a low intrinsic color. In addition, the process should ensure a safe and reproducible reaction.
  • amides of lower carboxylic acids by direct reaction of carboxylic acids with amines in a continuous process by only brief heating by irradiation with microwaves in a reaction tube whose longitudinal axis is in the propagation direction of the microwaves of a single-mode microwave applicator in technically relevant amounts let produce.
  • the microwave energy radiated into the microwave applicator is absorbed virtually quantitatively by the reaction mixture.
  • the inventive method also has a high level of safety in the implementation and provides a high reproducibility of the set reaction conditions.
  • the amides prepared by the process according to the invention show a high purity and low intrinsic coloration, which are not accessible without additional process steps, compared to conventional preparation processes.
  • the invention relates to a continuous process for the preparation of amides by reacting at least one carboxylic acid of the formula I.
  • R 3 is hydrogen or an optionally substituted alkyl group having 1 to 4 carbon atoms, with at least one amine of the formula II
  • R 1 and R 2 independently of one another represent hydrogen or a hydrocarbon radical having 1 to 100 carbon atoms, is converted to an ammonium salt, and this ammonium salt is subsequently irradiated under microwave irradiation in a reaction tube whose longitudinal axis is in the direction of propagation of the microwaves of a monomode Microwave applicator is converted to Carbonklamid.
  • Another object of the invention are carboxylic acid amides with a low metal content, prepared by reacting at least one carboxylic acid of formula I.
  • R 3 is hydrogen or an optionally substituted alkyl group having 1 to 4 carbon atoms, with at least one amine of the formula
  • R 1 and R 2 independently represent hydrogen or a hydrocarbon radical having 1 to 100 carbon atoms, to an ammonium salt and subsequent reaction of this ammonium salt to the carboxylic acid amide under microwave irradiation in a reaction tube whose longitudinal axis is in the propagation direction of the microwaves of a single-mode microwave applicator located.
  • R 3 is preferably a saturated alkyl radical having 1, 2, 3 or 4 C atoms. This can be linear or branched.
  • the carboxyl group can be bonded to a primary, secondary or, as in the case of pivalic acid, tertiary C atom.
  • the alkyl radical is unsubstituted
  • the alkyl radical carries one to nine, preferably one to five, for example two, three or four further substituents.
  • substituents may be, for example, C 1 -C 4 alkoxy such as, for example, methoxy, ester, amide, carboxyl, cyano, nitrile, nitro and / or C 5 -C 2 0 aryl groups, for example phenyl groups, with the proviso the substituents are stable under the reaction conditions and do not undergo side reactions such as elimination reactions.
  • the C 5 -C 2 o-aryl groups may in turn carry substituents.
  • Substituents may, for example, Ci-C2o-alkyl, C 2 -C 2 o-alkenyl, C 1 -C 5 -AIkOXy- such as methoxy, ester, amide, carboxyl, cyano, nitrile , and / or nitro groups.
  • the alkyl radical carries at most as many substituents as it has valencies.
  • the alkyl radical R 3 bears further carboxyl groups.
  • the inventive method is also suitable for the reaction of carboxylic acids with, for example, two or more carboxyl groups. In the reaction of such polycarboxylic acids with ammonia or primary amines according to the process of the invention, imides can also be formed.
  • Suitable aliphatic carboxylic acids are, for example, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pentanoic acid, iso-pentanoic acid, pivalic acid, succinic acid, butanetetracarboxylic acid, phenylacetic acid, (2-bromophenyl) acetic acid, (methoxyphenyl) acetic acid, (dimethoxyphenyl) acetic acid, 2-phenylpropionic acid , 3-phenylpropionic acid, 3- (4-hydroxyphenyl) propionic acid, 4-hydroxyphenoxyacetic acid and mixtures thereof.
  • Particularly preferred carboxylic acids according to the invention are formic acid, acetic acid and propionic acid, and also phenylacetic acid and its derivatives substituted on the aryl radical.
  • the process according to the invention is preferably suitable for the preparation of secondary amides, ie for the reaction of carboxylic acids with amines in which R 1 is a hydrocarbon radical having 1 to 100 carbon atoms and R 2 is hydrogen.
  • the inventive method is particularly preferred for
  • R 1 and / or R 2 independently of one another are an aliphatic radical.
  • This radical preferably has 1 to 24, _ o
  • the aliphatic radical may be linear, branched or cyclic. It can still be saturated or unsaturated.
  • the hydrocarbon radical may carry substituents. Such substituents may be, for example, hydroxy, C 1 -C 5 -alkoxy, alkoxyalkyl, cyano, nitrile, nitro and / or C 5 -C 2 o-aryl groups, for example phenyl radicals.
  • the Cs-C ⁇ o aryl groups can in turn optionally substituted with halogen atoms, C r C 2 o alkyl, C 2 -C 2 o-alkenyl, hydroxyl, Ci-C5 alkoxy such as methoxy, ester , Amide, cyano, nitrile, and / or nitro groups.
  • Particularly preferred aliphatic radicals are methyl, ethyl, hydroxyethyl, n-propyl, isopropyl, hydroxypropyl, n-butyl, isobutyl and tert-butyl, hydroxybutyl, n-hexyl, cyclohexyl, n-octyl, n-decyl, n-dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl and methylphenyl.
  • R 1 and / or R 2 are independently hydrogen, a Ci-C 6 alkyl, C 2 -C 6 -alkenyl or C 3 -C 6 cycloalkyl radical and especially an alkyl radical containing 1 , 2, or 3 C atoms. These radicals can carry up to three substituents.
  • R 1 and R 2 together with the nitrogen atom to which they are attached form a ring.
  • This ring preferably has 4 or more, such as 4, 5, 6 or more ring members.
  • Preferred further ring members are carbon, nitrogen, oxygen and sulfur atoms.
  • the rings in turn may carry substituents such as alkyl radicals.
  • Suitable ring structures are, for example, morpholinyl, pyrrolidinyl, piperidinyl, imidazolyl and azepanyl radicals.
  • R 1 and / or R 2 are independently an optionally substituted C 6 -C 2 aryl group or an optionally substituted heteroaromatic group having 5 to 12 ring members.
  • R 1 and / or R 2 independently of one another are an alkyl radical interrupted by heteroatoms. Particularly preferred heteroatoms are oxygen and nitrogen.
  • R 1 and / or R 2 independently of one another are preferably radicals of the formula III (III)
  • R 4 is an alkylene group having 2 to 6 carbon atoms and preferably 2 to
  • R 5 is hydrogen, a hydrocarbon radical having 1 to 24 C atoms or a group of the formula -NR 10 R 11 , n is a number between 2 and 50, preferably between 3 and 25 and in particular between 4 and 10 and R 10 , R 11 independently of one another represent hydrogen, an aliphatic radical having 1 to 24 C atoms and preferably 2 to 18 C atoms, an aryl group or heteroaryl group having 5 to 12 ring members, a poly (oxyalkylene) group having 1 to 50 poly (oxyalkylene) units, wherein the polyoxyalkylene units derived from alkylene oxide having 2 to 6 carbon atoms, or R 10 and R 11 together with the
  • R 1 and / or R 2 independently of one another are preferably radicals of the formula IV
  • D 6 is an alkylene group having 2 to 6 C atoms and preferably having 2 to 4 C atoms, such as, for example, ethylene, propylene or mixtures thereof, each R 7 is independently hydrogen, an alkyl or
  • Hydroxyalkyl radical having up to 24 carbon atoms such as 2 to 20 carbon atoms, a polyoxyalkylene radical - (R 4 -O) p -R 5 , or a polyiminoalkylene radical - [R 6 -N (R 7 )] q - (R 7 ), wherein R 4 , R 5 , R 6 and R 7 have the meanings given above and q and p are independently from 1 to 50 and m is a number from 1 to 20 and preferably 2 to 10 such as three, four , five or six stands.
  • the radicals of the formula IV preferably contain 1 to 50, in particular 2 to 20, nitrogen atoms.
  • one or more amino groups are converted into the carboxylic acid amide.
  • the primary amino groups can also be converted into imides.
  • nitrogen-containing compounds which split off ammonia gas on heating instead of ammonia.
  • nitrogen-containing compounds are urea and formamide.
  • Suitable amines are ammonia, methylamine, ethylamine, ethanolamine, propylamine, propanolamine, butylamine, hexylamine, cyclohexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, dimethylamine, diethylamine, diethanolamine, ethylmethylamine, di-n-propylamine, di -iso-propylamine, dicyclohexylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, dioctadedcylamine, benzylamine, phenylethylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and mixtures thereof.
  • dimethylamine, diethylamine, di-n-propylamine, di-iso-propylamine and ethylmethylamine are particularly preferred.
  • the process is particularly suitable for preparing N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylpropionamide, N, N-dimethylbutyramide, N, N-diethylformamide N, N-diethylacetamide, N, N-diethylpropionamide, N, N-diethylbutyramide , N, N-dipropylacetamide, N, N-dimethyl (phenyl) acetic acid amide, N, N-dimethyl (p-methoxyphenyl) acetic acid amide and N, N-dimethyl-2-phenlypropionic acid.
  • aliphatic carboxylic acid and amine can be reacted with one another in any ratio.
  • the reaction between carboxylic acid and amine preferably takes place with molar ratios of from 10: 1 to 1: 100, preferably from 2: 1 to 1:10, especially from 1.2: 1 to 1: 3, in each case based on the molar equivalents of carboxyl groups.
  • carboxylic acid and amine are used equimolar.
  • R 1 and / or R 2 is one with one or more
  • Hydroxyl-substituted hydrocarbon radical the reaction between carboxylic acid and amine with molar ratios of 1: 1 to 1: 100, preferably from 1: 1, 001 to 1:10 and especially from 1: 1, 01 to 1: 5 such as from 1: 1, 1 to 1: 2, in each case based on the molar equivalents of carboxyl groups and amino groups in the reaction mixture.
  • the inventive preparation of the amides is carried out by reacting carboxylic acid and amine to the ammonium salt and subsequent irradiation of the Salt with microwaves in a reaction tube whose longitudinal axis is in the propagation direction of the microwaves in a single-mode microwave applicator.
  • the irradiation of the salt with microwaves preferably takes place in a largely microwave-transparent reaction tube, which is located within a waveguide connected to a microwave generator.
  • the reaction tube is aligned axially with the central axis of symmetry of the waveguide.
  • the acting as a microwave applicator waveguide is preferred as
  • Cavity resonator formed. Further preferably, the microwaves not absorbed in the waveguide are reflected at its end.
  • the microwave applicator as a reflection-type resonator, a local increase in the electric field strength is achieved with the same power supplied by the generator and an increased energy utilization.
  • the cavity resonator is preferably operated in mode n E i 0, where n is an integer and represents the number of field maxima of the microwave along the central axis of symmetry of the resonator.
  • the electric field is in the direction of the central axis of symmetry of the
  • Cavity resonator directed. It has a maximum in the area of the central axis of symmetry and decreases to the lateral surface to the value zero. This field configuration is rotationally symmetric about the central axis of symmetry.
  • the length of the resonator is selected relative to the wavelength of the microwave radiation used.
  • N is preferably an integer from 1 to 200, particularly preferably from 2 to 100, in particular from 4 to 50 and especially from 3 to 20, for example 3, 4, 5, 6, 7 or 8.
  • the irradiation of the microwave energy into the waveguide acting as a microwave applicator can take place via suitably dimensioned holes or slots.
  • the irradiation of the ammonium salt with microwaves in a reaction tube which is located in a waveguide with coaxial transition of the microwaves.
  • particularly preferred microwave devices are made of a cavity resonator, a coupling device for coupling a microwave field in the
  • Cavity resonator and constructed with one opening at two opposite end walls for passing the reaction tube through the resonator.
  • the coupling of the microwaves in the cavity resonator is preferably carried out via a coupling pin, which projects into the cavity resonator.
  • the coupling pin is preferably shaped as a preferably metallic inner conductor tube functioning as a coupling antenna. In a particularly preferred embodiment of this coupling pin protrudes through one of the frontal openings into the cavity resonator.
  • the reaction tube connects to the inner conductor tube of the coaxial transition and in particular it is guided through its cavity into the cavity resonator.
  • the reaction tube is aligned axially with a central axis of symmetry of the cavity resonator, for which purpose the cavity resonator preferably each has a central opening on two opposite end walls for passing the reaction tube.
  • the feeding of the microwaves in the coupling pin or in the acting as a coupling antenna inner conductor tube can be done for example by means of a coaxial connecting cable.
  • the microwave field is supplied to the resonator via a waveguide, wherein the protruding from the cavity resonator end of the coupling pin is guided into an opening which is located in the wall of the waveguide in the waveguide and the waveguide takes microwave energy and in the Resonator couples.
  • the irradiation of the salt with microwaves in a microwave-transparent reaction tube which is axially symmetrical in a Eoi n round waveguide with coaxial transition of the microwaves.
  • the reaction tube is through the cavity of a Coupling antenna acting inner conductor tube is guided into the cavity resonator.
  • Microwave generators such as the magnetron, the klystron and the gyrotron are known in the art.
  • the reaction tubes used for carrying out the method according to the invention are preferably made of largely microwave-transparent, high-melting material.
  • Non-metallic reaction tubes are particularly preferably used.
  • Substantially microwave-transparent materials are understood here which absorb as little microwave energy as possible and convert it into heat.
  • the dielectric loss factor tan ⁇ is defined as the ratio of dielectric loss ⁇ "and dielectric constant ⁇ '. Examples of tan ⁇ values of various materials Microwave-assisted Organic Synthesis, Elsevier 2005. For example, in D. Bogdal reproduced.
  • suitable reaction tubes Materials with tan ⁇ values measured at 2.45 GHz and 25 ° C. of below 0.01, in particular below 0.005 and especially below 0.001 are preferred .
  • Temperature-stable plastics such as in particular fluoropolymers such as Teflon, and technical Plastics such as polypropylene, or polyaryletherketones such as glass fiber reinforced polyetheretherketone (PEEK) are suitable as tube materials.
  • PEEK glass fiber reinforced polyetheretherketone
  • reaction tubes have an inner diameter of one millimeter to about 50 cm, especially between 2 mm and 35 cm, for example between 5 mm and 15 cm.
  • Reaction tubes are understood here to be vessels whose ratio of length to diameter is greater than 5, preferably between 10 and 100,000, particularly preferably between 20 and 10,000, for example between 30 and 1,000.
  • the length of the reaction tube is understood here as the distance of the reaction tube on which the microwave irradiation takes place.
  • baffles and / or other mixing elements can be installed.
  • Eo-i cavity resonators preferably have a diameter corresponding to at least half the wavelength of the microwave radiation used.
  • the diameter of the cavity resonator is the 1, 0- to
  • the Eor cavity resonator has a round cross-section, which is also referred to as an EorRundhohlleiter. Particularly preferably it has a cylindrical shape and especially a circular cylindrical shape.
  • the reaction tube is usually provided at the inlet with a metering pump and a pressure gauge and at the outlet with a pressure holding device and a heat exchanger. This allows reactions in a very wide range of pressure and temperature.
  • reaction of amine and carboxylic acid to form the ammonium salt can be carried out continuously, batchwise or else in semi-batch processes O
  • the preparation of the ammonium salt can be carried out in an upstream (semi) -batch process, such as in a stirred tank.
  • the ammonium salt is preferably generated in situ and not isolated.
  • the educts amine and carboxylic acid, both independently of one another optionally diluted with solvent, are mixed shortly before they enter the reaction tube.
  • the educts are fed to the process according to the invention in liquid form.
  • higher-melting and / or higher-viscosity starting materials for example in the molten state and / or with solvent, for example, can be used as solution, dispersion or emulsion.
  • a catalyst can be added to one of the educts or else to the educt mixture before it enters the reaction tube.
  • Solid, pulverulent and heterogeneous systems can also be reacted by the process according to the invention, with only corresponding technical devices for conveying the reaction mixture being required.
  • the ammonium salt may be fed into the reaction tube either at the end guided through the inner conductor tube, as well as at the opposite end.
  • length of the irradiation zone (this is understood to mean the distance of the reaction tube in which the reaction mixture
  • the reaction conditions are adjusted so that the maximum reaction temperature is reached as quickly as possible and the residence time at maximum temperature remains so short that as few side or subsequent reactions as possible occur.
  • the reaction mixture can be passed through the reaction tube several times to complete the reaction, optionally after intermediate cooling. In many cases, it has proven useful if the reaction product immediately after leaving the reaction tube z. B. is cooled by jacket cooling or relaxation. With slower reactions, it has often proven useful to keep the reaction product after leaving the reaction tube for a certain time at the reaction temperature.
  • the advantages of the method according to the invention lie in a very uniform irradiation of the reaction material in the center of a symmetrical microwave field within a reaction tube whose longitudinal axis is in the propagation direction of the microwaves of a single-mode microwave applicator, and in particular within a EorHohlraumresonators example with coaxial transition.
  • the reactor design according to the invention allows reactions to be carried out even at very high pressures and / or temperatures. By increasing the temperature and / or pressure, a clear increase in the degree of conversion and yield is also observed in comparison to known microwave reactors, without causing undesired side reactions and / or discoloration.
  • a very high efficiency is achieved in utilizing the microwave energy radiated into the cavity resonator, which is usually more than 50%, often more than 80%, partly over 90% and in special cases more than 95%, for example over 98% of the radiated microwave power and thus provides economic as well as environmental advantages over conventional manufacturing methods as well as prior art microwave methods.
  • the inventive method also allows a controlled, safe and reproducible reaction. Since the reaction mixture is moved in the reaction tube parallel to the direction of propagation of the microwaves, known overheating phenomena by uncontrollable field distributions, which lead to local overheating by changing intensity of the field, for example in wave crests and nodes, by the flow of the
  • Ammonium salt in the microwave field a very extensive amidation with conversions in general of over 80%, often over 90% such as more than 95% based on the component used in the deficit occurs, without formation of appreciable amounts of by-products.
  • these ammonium salts in a flow tube of the same dimensions under thermal jacket heating extremely high wall temperatures are required to achieve suitable reaction temperatures, which led to the formation of colored species, but cause only minor amide formation at the same time interval.
  • the products produced by the process according to the invention have very low metal contents without the need for further processing of the crude products.
  • the metal contents of the products produced by the process according to the invention based on iron as the main element are usually below 25 ppm, preferably below 15 ppm, especially below 10 ppm, such as between 0.01 and 5 ppm iron.
  • the temperature rise caused by the microwave irradiation is limited to a maximum of 500 ° C., for example by controlling the microwave intensity, the flow rate and / or by cooling the reaction tube, for example by a stream of nitrogen.
  • the implementation of the reaction has proven particularly useful at temperatures between 150 and 400 ° C. and especially between 180 and 300 ° C., for example at temperatures between 200 and 270 ° C.
  • the duration of the microwave irradiation depends on various factors such as the geometry of the reaction tube, the radiated microwave energy, the specific reaction and the desired degree of conversion. Usually, the microwave irradiation over a Period of less than 30 minutes, preferably between 0.01 seconds and 15 minutes, more preferably between 0.1 seconds and 10 minutes and in particular between one second and 5 minutes, for example between 5 seconds and 2 minutes.
  • the intensity (power) of the microwave radiation is adjusted so that the reaction material when leaving the cavity resonator has the desired maximum temperature.
  • the reaction product is cooled as soon as possible after completion of the microwave irradiation to temperatures below 120 0 C, preferably below 100 0 C and especially below 60 0 C.
  • the reaction is carried out at pressures between 0.01 and 500 bar and more preferably between 1 bar (atmospheric pressure) and 150 bar and especially between 1, 5 bar and 100 bar such as between 3 bar and 50 bar.
  • Working under elevated pressure has proven particularly useful, the starting materials or products, the optionally present solvent and / or above the reaction water formed during the reaction being worked above the boiling point (at atmospheric pressure). More preferably, the pressure is set so high that the reaction mixture remains in the liquid state during microwave irradiation and does not boil.
  • an inert protective gas such as nitrogen, argon or helium.
  • the reaction is accelerated or completed in the presence of dehydrating catalysts.
  • dehydrating catalysts Preferably, one works in the presence of an acidic inorganic, organometallic or organic catalyst or mixtures of several of these catalysts.
  • acidic inorganic catalysts for the purposes of the present invention are sulfuric acid, phosphoric acid, phosphonic acid, hypophosphorous acid, aluminum sulfate hydrate, alum, acidic silica gel and acidic aluminum hydroxide.
  • aluminum compounds of the general formula AI (OR 15 ) 3 and titanates of the general formula Ti (OR 15 ) 4 can be used as acidic inorganic catalysts, wherein the radicals R 15 may be the same or different and are independently selected from CiC-io Alkyl radicals, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl , 1, 2-dimethylpropyl, iso-amyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-Ethylhexy, n-nonyl or n-decyl, C3-Ci2 cycloalkyl, for example cyclopropyl
  • Preferred acidic organometallic catalysts are, for example, selected from dialkyltin oxides (R 15 ) 2 SnO, where R 15 is as defined above.
  • R 15 dialkyltin oxides
  • a particularly preferred representatives of acidic organometallic catalysts is di-n-butyltin oxide, which is commercially available as so-called Oxo-tin or as Fascat ® brands.
  • Preferred acidic organic catalysts are acidic organic compounds with, for example, phosphate groups, sulfonic acid groups, sulfate groups or phosphonic acid groups.
  • Particularly preferred sulfonic acids contain at least one sulfonic acid group and at least one saturated or unsaturated, linear, branched and / or cyclic hydrocarbon radical having 1 to 40 carbon atoms and preferably having 3 to 24 carbon atoms.
  • Particularly preferred are aromatic sulfonic acids, especially alkylaromatic monosulfonic acids having one or more dC ⁇ ⁇ -alkyl radicals and in particular those having C3-C22-alkyl radicals.
  • Suitable examples are methanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, 2-mesitylenesulfonic acid, 4-ethylbenzenesulfonic acid, isopropylbenzenesulfonic acid, 4-butylbenzenesulfonic acid, 4-octylbenzenesulfonic acid; Dodecylbenzenesulfonic acid, didodecylbenzenesulfonic acid, naphthalenesulfonic acid.
  • Acidic ion exchangers can also be used as acidic organic catalysts, for example poly (styrene) sulfonic acid groups which are crosslinked with about 2 mol% of divinylbenzene.
  • titanates of the general formula Ti (OR 15 ) 4 and especially titanium tetrabutylate and titanium tetraisopropylate are particularly preferred for carrying out the process according to the invention.
  • acidic inorganic, organometallic or organic catalysts according to the invention 0.01 to 10% by weight, preferably 0.02 to 2% by weight, of catalyst is used. In a particularly preferred embodiment, working without a catalyst.
  • the microwave irradiation is carried out in the presence of acidic solid catalysts.
  • the solid catalyst is suspended in the optionally mixed with solvent ammonium salt or advantageously the optionally with solvent-added ammonium salt passed through a fixed bed catalyst and exposed to microwave radiation.
  • Suitable solid catalysts are, for example, zeolites, silica gel, montmorillonite and (partially) crosslinked polystyrenesulphonic acid, which may optionally be impregnated with catalytically active metal salts.
  • Suitable acidic ion exchanger based on polystyrene sulfonic acids that can be used as solid phase catalysts are for example available from the company Rohm & Haas under the trademark Amberlyst ®.
  • Suitable solvents for the process according to the invention are, in particular, solvents having ⁇ " values below 10, such as N-methylpyrrolidone, N, N-dimethylformamide or acetone, and in particular solvents having ⁇ "values below 1.
  • EXAMPLES for particularly preferred solvents with ⁇ "values below 1 are aromatic and / or aliphatic hydrocarbons such as toluene, xylene, ethylbenzene, tetralin, hexane, cyclohexane, decane, pentadecane, decalin and commercial hydrocarbon mixtures such as gasoline fractions, kerosene, solvent naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxs ol, ® isopar and ® Shellsol types.
  • Solvent mixtures which have ⁇ "values preferably below 10 and especially below 1 are equally preferred for carrying out the process according to the invention.
  • the process according to the invention can also be carried out in solvents having higher ⁇ "values of, for example, 5 and higher, in particular with ⁇ " values of 10 and higher.
  • ⁇ values of, for example, 5 and higher
  • ⁇ values of 10 and higher.
  • reaction mixture is preferably between 2 and 95 wt .-%, especially between 5 and 90 wt .-% and in particular between 10 and 75 wt .-%, such as between 30 and 60 wt .-%.
  • the reaction is carried out solvent-free.
  • Microwaves are electromagnetic waves having a wavelength between about 1 cm and 1 m and frequencies between about 300 MHz and 30 GHz. This frequency range is suitable in principle for the method according to the invention.
  • microwave radiation with the frequencies released for industrial, scientific and medical applications is preferably used, for example with frequencies of 915 MHz, 2.45 GHz, 5.8 GHz or 27.12 GHz.
  • microwave power to be radiated into the cavity resonator for carrying out the method according to the invention is in particular dependent on the geometry of the reaction tube and thus of the
  • Reaction volume and the duration of the required irradiation It is usually between 200 W and several 100 kW and in particular between 500 W and 100 kW such as between 1 kW and 70 kW. It can be generated by one or more microwave generators.
  • the reaction is carried out in a pressure-resistant inert tube, wherein the water of reaction forming and optionally starting materials and, if present, solvents lead to a pressure build-up.
  • the excess pressure can be used by relaxation for volatilization and separation of water of reaction, excess starting materials and, if appropriate, solvents and / or for cooling the reaction product.
  • the water of reaction formed is after cooling and / or relaxation by conventional methods such as phase separation, distillation stripping, flashing and / or absorption separated.
  • amides prepared via the route according to the invention are obtained in a sufficient purity for further use.
  • they can be further purified by customary purification methods such as, for example, distillation, recrystallization, filtration or chromatographic methods.
  • the inventive method allows a very fast, energy-saving and cost-effective production of amides of lower carboxylic acids in high yields and high purity in large quantities. Due to the very uniform irradiation of the ammonium salt in the center of the rotationally symmetric microwave field, it allows a safe, controllable and reproducible reaction. It is achieved by a very high efficiency in the utilization of the radiated microwave energy, the known manufacturing process significantly superior efficiency. This process does not generate significant amounts of by-products. Such rapid and selective reactions can not be achieved by conventional methods and were not to be expected by heating to high temperatures alone. The products produced by the process according to the invention are often so pure that no further preparation or post-processing steps are required. Examples
  • Cavity resonator passed through the ceramic tube through the cavity of a functioning as a coupling antenna inner conductor tube.
  • the microwave field generated by a magnetron with a frequency of 2.45 GHz was coupled by means of the coupling antenna in the cavity resonator (Eoi cavity applicator, single mode).
  • the microwave power was adjusted over the duration of the experiment in such a way that the desired temperature of the reaction mixture was kept constant at the end of the irradiation zone.
  • the microwave powers mentioned in the test descriptions therefore represent the time average of the irradiated microwave power.
  • the temperature measurement of the reaction mixture was carried out directly after leaving the reaction zone (about 15 cm distance in an insulated stainless steel capillary, 0 1 cm) by means of PtIOO temperature sensor. Microwave energy not directly absorbed by the reaction mixture was reflected at the end face of the cavity resonator opposite the coupling antenna; the microwave energy which was not absorbed by the reaction mixture during the return and was reflected back in the direction of the magnetron was conducted by means of a prism system (circulator) into a vessel containing water. From the difference between incident energy and heating of this water load, the microwave energy introduced into the reaction mixture was calculated
  • reaction mixture was placed in the reaction tube under such a working pressure, which was sufficient to all educts and products or
  • ammonium salts prepared from carboxylic acid and amine were pumped through the reaction tube at a constant flow rate and the residence time in the Irradiation zone adjusted by modifying the flow rate.
  • the products were analyzed by means of 1 H-NMR spectroscopy at 500 MHz in CDCl 3 .
  • the determination of iron contents was carried out by atomic absorption spectroscopy.
  • the ammonium salt thus obtained was continuously pumped through the reaction tube at a working pressure of 35 bar at 5.0 l / h and a
  • the preparation of the ammonium salt was carried out analogously to the method described in Example 1. There were 2.4 kg (40 mol) of acetic acid and 1, 9 kg (42 mol) of dimethylamine used.
  • the ammonium salt thus obtained was continuously pumped through the reaction tube at 4.2 l / h at a working pressure of 30-35 bar and exposed to a microwave power of 1.75 kW, of which 88% was absorbed by the reaction mixture.
  • the residence time of the reaction mixture in the irradiation zone was about 40 seconds. At the end of the reaction tube, the reaction mixture had a temperature of 241 0 C.
  • the preparation of the ammonium salt was carried out analogously to the method described in Example 1. There were used 3.7 kg (50 mol) of propionic acid and 4.5 kg (100 mol) of dimethylamine.
  • the ammonium salt thus obtained was continuously pumped through the reaction tube at a working pressure of 30 bar at 3.8 l / h and subjected to a microwave power of 1.90 kW, of which 90% was absorbed by the reaction mixture.
  • the residence time of the reaction mixture in the irradiation zone was about 45 seconds.
  • the reaction mixture had a temperature of 260 ° C.
  • Dry ice cooling was used to condense 2.7 kg of dimethylamine (60 mol) from a storage bottle into a cold trap.
  • 10 kg of 4-methoxyphenylacetic acid (60 mol) were introduced into a 10 l Büchi stirred autoclave with gas inlet tube, mechanical stirrer, internal thermometer and pressure equalization and melted at about 100 ° C.
  • gaseous dimethylamine was introduced slowly through the gas inlet tube in the stirred autoclave directly into the acid melt.
  • the 4-methoxyphenylacetic acid N, N-dimethylammonium salt formed.
  • the resulting molten ammonium salt (95 ° C.) was pumped through the reaction tube continuously at 3.0 l / h at a working pressure of about 25 bar and subjected to a microwave power of 1.95 kW, of which 95% was absorbed by the reaction mixture.
  • the residence time of the reaction mixture in the irradiation zone was about 57 seconds.
  • the reaction mixture had a temperature of 245 0 C.
  • a melt of the 4-methoxyphenylacetic acid N, N-dimethylammonium salt was prepared by the method described in the preceding example. To this melt (400 g), 400 g of toluene was added and the mixture heated to 150 0 C. With the aid of a water separator, the water of reaction formed during the amidation was removed from the system. After refluxing for 48 hours, toluene was distilled off and the conversion was determined. Based on the acid used, a conversion of less than 2% was found. In addition, there was a marked darkening of the reaction mixture.
  • Example 7 Preparation of 4-methoxyphenylacetic acid N, N-dimethylamide by thermal condensation in the presence of iron filings (comparative example)
  • Example 6 The experiment according to Example 6 was repeated, wherein the reaction mixture 1 g of iron filings were added. Again, the mixture was boiled at the boiling point of toluene for 48 hours on a water separator.
  • the reaction mixture contained 85 ppm of dissolved iron and had a black-brown color.
  • Example 8 Preparation of 4-methoxyphenylacetic acid N, N-dimethylamide in a batch single-mode laboratory microwave apparatus
  • a melt of the 4-methoxyphenylacetic acid N, N-dimethylammonium salt was prepared by the method described in the preceding example. From this melt 2 ml were included pressure-tight into a pressure-resistant vial and placed in the microwave cavity of a 'Biotage Initiator TM "laboratory microwave instrument. The reaction mixture was then heated by applying 300 W microwave power within one minute to 235 0 C, thereby formed At the end of the heat-up time, another 300 seconds (5 minutes) of controlled power was applied to the sample, adjusting the performance so that the temperature of the reaction mixture remained constant at 235 ° C. Referred to on the acid used, a conversion of 11% was found in the crude product.

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AU2009231125A1 (en) 2009-10-08
EA018179B1 (ru) 2013-06-28
CA2720370A1 (en) 2009-10-08
DE102008017218A1 (de) 2009-10-08
CN101984755B (zh) 2014-11-12
EA201001115A1 (ru) 2010-12-30
DE102008017218B4 (de) 2011-09-22
WO2009121490A1 (de) 2009-10-08
KR20100135719A (ko) 2010-12-27

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