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WO2006136571A1 - Procede de production en continu d'une amine - Google Patents

Procede de production en continu d'une amine Download PDF

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Publication number
WO2006136571A1
WO2006136571A1 PCT/EP2006/063384 EP2006063384W WO2006136571A1 WO 2006136571 A1 WO2006136571 A1 WO 2006136571A1 EP 2006063384 W EP2006063384 W EP 2006063384W WO 2006136571 A1 WO2006136571 A1 WO 2006136571A1
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Prior art keywords
preparation
reacting
amine
ammonia
reaction
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German (de)
English (en)
Inventor
Frank Haese
Joachim Wulff-Döring
Ulrich KÖHLER
Peter Gaa
Frank-Friedrich Pape
Johann-Peter Melder
Manfred Julius
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
    • C07D295/033—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
    • C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered

Definitions

  • the present invention relates to a process for the continuous production of an amine by reacting a primary or secondary alcohol, aldehyde and / or ketone with hydrogen and a nitrogen compound selected from the group ammonia, primary and secondary amines, at a temperature in the range of 80 to 350 0 C in the presence of a zirconium dioxide-containing catalyst.
  • EP-A-257 443 (BASF AG) relates to a process for the preparation of trialkylamines (for example dimethylethylamine) by reacting ammonia with alcohols in the presence of alkali metal hydroxide in the liquid phase over a catalyst containing essentially only copper.
  • trialkylamines for example dimethylethylamine
  • EP-A-542 039 (BASF AG) describes a process for the preparation of cyclic amines, e.g. N.N-dimethylcyclohexylamine, by reductive amination of ketones on zeolites in the gas phase in a shell-and-tube reactor under isothermal conditions.
  • EP-A-227 904 (BASF AG) teaches the Hersannon of Dimethyiethylamin or N 1 N- Dimethyicyclohexy ⁇ amin in the liquid phase by reacting dimethylamine with cyclohexanol in the presence of alkali metal hydroxide and a catalyst which essentially comprises as active metal only copper or a pure Copper catalyst is.
  • the method should enable better yields, space-time yields (RZA) and / or selectivities.
  • RZA space-time yields
  • Space-time yields are given in 'product amount / (catalyst volume • time)' (kg / (i K a t • h)) and / or 'product amount / (reactor volume • time)' (kg / (l R ⁇ a ktor • H)].
  • the problem could be solved by operating the synthesis in the liquid phase or in the gas phase on a bimetallic palladium / petratin contact with ZrO 2 support .
  • a process for continuously preparing an amine by reacting a primary or secondary alcohol, aldehyde and / or ketone with hydrogen and a nitrogen compound selected from the group consisting of ammonia, primary and secondary amines, at a temperature in the range of 80 to 350 0 C. in the presence of a zirconium dioxide-containing catalyst, which is characterized in that the catalytically active material of the catalyst prior to its reduction with hydrogen
  • zirconium dioxide 90 to 99.8% by weight zirconium dioxide (ZrO 2 ),
  • the starting materials are targeted, preferably in a circulating gas stream, vaporized and fed to the reactor in gaseous form.
  • Suitable amines for a gas-phase synthesis are amines which, because of their boiling points and the boiling points of their educts, can be held in the gas phase within the scope of the process parameters.
  • the recycle gas serves to evaporate the reactants and to react as reactants for the amination.
  • the starting materials (alcohol, aldehyde and / or ketone, hydrogen and the nitrogen compound) are evaporated in a circulating gas stream and fed into the reactor in gaseous form.
  • the educts (alcohol, aldehyde and / or ketone, the nitrogen compound) can also be evaporated as aqueous solutions and passed with the circulating gas stream on the catalyst bed.
  • Preferred reactors are tubular reactors. Examples of suitable reactors with recycle gas stream are found in Ultmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. B 4, pages 199-238, "Fäxed-Bed Reactors".
  • the reaction is advantageously carried out in a tube bundle reactor or in a monostane system.
  • the tubular reactor in which the reaction takes place can consist of a series connection of several (eg two or three) individual tubular reactors.
  • an intermediate feed of feed containing the educt and / or ammonia and / or H 2
  • circulating gas and / or reactor discharge from a downstream reactor is advantageously possible here.
  • the circulating gas quantity is preferably in the range from 40 to 1500 m 3 (at operating pressure) / [m 3 catalyst (bulk volume) • h], in particular in the range from 100 to 700 m 3 (at operating pressure) / [m 3 catalyst (bulk volume). H].
  • the cycle gas preferably contains at least 10, especially 50 to 100, especially 80 to 100, vol.% H 2 .
  • the catalysts are preferably used in the form of catalysts which consist only of catalytically active material and optionally of a deformation aid (such as graphite or stearic acid), if the catalyst is used as a molding, ie no further catalytically active substances contain.
  • a deformation aid such as graphite or stearic acid
  • the oxidic support zirconium dioxide (ZrO 2 ) is considered as belonging to the catalytically active material.
  • the catalysts are used in such a way that the catalytically active mass ground to powder is introduced into the reaction vessel or that the catalysed active composition after grinding, mixing with molding aids, shaping and heat treatment as a shaped catalyst body - for example as tablets, spheres, rings , Extrudates (eg strands) - in the reactor arranges.
  • the concentration data (in% by weight) of the components of the catalyst are in each case - unless stated otherwise - on the kataiytisch active mass of the finished catalyst after the last heat treatment and before its reduction with hydrogen.
  • the catalytically active mass of the catalyst is calculated as the sum of the masses of the catalytic table active ingredients and the above-mentioned catalyst support materials and contains essentially the following components:
  • Zirconia Zirconia (ZrO 2 ), oxygenated compounds of palladium, and oxygenates of platinum.
  • ingredients of the catalytically active composition is usually 70 to 100% by weight, preferably 80 to 100% by weight, particularly preferably 90 to 100% by weight, especially> 95% by weight, very particularly> 98% by weight , in particular> 99 wt .-%, for example particularly preferably 100% by weight.
  • the catalytically active composition of the catalysts used in the process according to the invention may further contain one or more elements (oxidation state 0) or their inorganic or organic compounds selected from the groups I A to Vl A and I B to VIi B and VIII of the Periodic Table.
  • transition metals such as Co or CoO, Re or rhenium oxides, Mn or MnO 2 , Mo or molybdenum oxides, W or tungsten oxides, Ta or tantalum oxides, Nb or niobium oxides or niobium oxalate , V or vanadium oxides or vanadyl pyrophosphate; Lanthanides, such as Ce or CeO 2 or Pr or Pr 2 O 3 ; Alkali metal oxides, such as Na 2 O; alkali metal; Alkaline earth metal oxides, such as SrO; Alkaline earth metacarbonates such as MgCO 3 , CaCO 3 and BaCO 3 ; Boron oxide (B 2 O 3 ).
  • transition metals such as Co or CoO, Re or rhenium oxides, Mn or MnO 2 , Mo or molybdenum oxides, W or tungsten oxides, Ta or tantalum oxides, Nb or niobium oxides or niobium
  • the catalytically active composition of the catalysts used in the process according to the invention preferably contains no ruthenium, no copper, no cobalt, no iron and / or no nickel.
  • the catalytically active composition of the catalysts used in the process according to the invention contains 90 to 99.8 wt .-%, preferably 98 to 99.6 wt .-%, particularly preferably 98.8 to 99 after their last heat treatment and before its reduction with hydrogen, 2% by weight zirconium dioxide (ZrO 2 ),
  • Various processes are possible for the preparation of the catalysts used in the process according to the invention. Here are, for example, the known precipitation methods to call.
  • the catalysts used in the process according to the invention can in particular be prepared by impregnation of zirconium dioxide (ZrO 2 ) which is present, for example, in the form of powders or shaped articles, such as extrudates, tablets, spheroid or rings.
  • ZrO 2 zirconium dioxide
  • the zirconia is used, for example, in the monoclinic or tetragonal form, preferably in the monoclinic form.
  • the impregnation is also carried out by the usual methods, such as. B. A. Stiles, Cataiyst Manufacture Laboratory and Commerciai Preparations, Marcel Dekker, New York (1983), by applying a respective metal salt solution in one or more impregnation stages, wherein as Metailsaize z. B. corresponding nitrates, acetates or chlorides can be used. The mass is dried after the impregnation and optionally calcined.
  • the impregnation can be carried out by the so-called "incipient wetness" method, in which the zirconium dioxide is moistened in accordance with its water absorption capacity to a maximum of saturation with the impregnation solution.
  • the impregnation can also be done in supernatant solution.
  • multi-stage impregnation processes it is expedient to dry between individual impregnation steps and optionally to calcine.
  • the multi-step impregnation is advantageous to apply especially when the zirconium dioxide is to be applied with a larger amount of metal.
  • the catalyst is suitably conditioned, whether it is adjusted by grinding to a certain particle size or that it after grinding with molding aids such as graphite or stearic acid mixed, by means of a press to formations, z.
  • molding aids such as graphite or stearic acid mixed
  • the Ten> pertemperaturen preferably correspond to the temperatures during Caicintician.
  • the catalysts prepared in this way contain the catalytically active metals in the form of a mixture of their oxygenated compounds, i. especially as oxides and mixed oxides.
  • the catalysts prepared in this way are stored as such and possibly traded. Before being used as catalysts, they are usually prereduced. However, they can also be used without prereduction, in which case they are reduced under the conditions of the hydrogenating amination by the hydrogen present in the reactor.
  • the catalysts are preferably initially at 150 to 200 0 C over a period of eg 12 Ü exposed hydrogen-nitrogen atmosphere to 20 hours, and then a still up to about 24 hours at preferably 200 to 400 0 C in a hydrogen atmosphere treated.
  • some of the oxygen-containing metal compounds present in the catalysts are reduced to the corresponding metals so that they are present together with the different oxygen compounds in the active form of the catalyst.
  • the Pd / Pt / ZrO 2 catalysts disclosed in EP-A-701 995 (BASF AG) are particularly preferably used in the process according to the invention.
  • the process according to the invention is carried out continuously, the catalyst preferably being arranged as a fixed bed in the reactor.
  • the catalyst preferably being arranged as a fixed bed in the reactor.
  • both an inflow of the fixed catalyst bed from above and from below is possible.
  • the gas flow is adjusted by temperature, pressure and amount so that even higher-boiling (high-boiling) reaction products remain in the gas phase.
  • the aminating agent can be used in stoichiometric, lower or superstoichometric amounts.
  • the amine is preferably used in about stoichiometric amount or slightly super-stoichiometric amount per mole to be aminated alcoholic hydroxyl group, aldehyde group or keto group used.
  • the amine component (nitrogen compound) is preferably in the 0.90 to 100-fold molar amount, in particular in the 1, 0 to 10-fold molar amount, in each case based on the / used alcohol, aldehyde and / or ketone used.
  • ammonia is generally employed with a 1.5 to 250-fold, preferably 2 to 100-fold, in particular 2 to 10-fold, molar excess per mole of alcoholic hydroxyl group, aldehyde group or keto group to be converted. Higher excesses of both ammonia and primary or secondary amines are possible.
  • an amount of exhaust gas from 5 to 800 standard cubic meters / h, in particular 20 to 300 standard cubic meters / h, driven.
  • the starting materials are passed simultaneously in the liquid phase at pressures of generally from 5 to 30 MPa (50 to 300 bar), preferably from 5 to 25 MPa, more preferably from 15 to 25 MPa, and temperatures of generally 80 to 350 0 C, especially 100 to 300 0 C, preferably 120 to 270 0 C, particularly preferably 130 to 250 0 C, in particular 170 to 230 0 C, including hydrogen over the catalyst, the usually located in a preferably heated from the outside fixed bed reactor. It is both a trickle mode and a sumping way possible.
  • the catalyst loading is at least in the range from 0.05 to 5, preferably 0.1 to 2, more preferably 0.2 to 0.6, kg of alcohol, aldehyde or ketone per liter of catalyst (bulk volume) and hour.
  • a dilution of the starting materials with a suitable solvent such as tetrahydrofuran, dioxane, N-methylpyrrolidone or Ethytenglykoidimethylether done. It is expedient to heat the reactants before they are introduced into the reaction vessel, preferably to the reaction temperature.
  • the gaseous educts (alcohol, aldehyde or ketone plus ammonia or amine) in a gas stream chosen for evaporation sufficiently large, preferably hydrogen, at pressures of generally 0.1 to 40 MPa (1 to 400 bar), preferably 0.1 to 10 MPa, more preferably 0.1 to 5 MPa, in the presence of hydrogen passed over the catalyst.
  • the temperatures for the amination of alcohols are generally 80 to 350 0 C, especially 100 to 300 0 C, preferably 120 to 270 ⁇ C, particularly preferably 160 to 250 0 C.
  • the reaction temperatures in the hydrogenating amalgamation of aldehydes and ketones are generally 80 to 350 0 C, especially 90 to 300 0 C, preferably 100 to 250 0 C. It is there both an inflow of the fixed catalyst bed from above and from below possible.
  • the required gas stream is preferably obtained by a cycle gas method.
  • the catalyst loading is generally in the range of 0.01 to 2, preferably 0.05 to 0.5, kg of alcohol, aldehyde or ketone per liter of catalyst ⁇ bulk volume) and hour.
  • the hydrogen is generally added to the reaction in an amount of from 5 to 400 l, preferably in an amount of from 50 to 200 l per mol of alcohol, aldehyde or ketone component, the liter data in each case being converted to standard conditions (STP ).
  • the amination of aldehydes or ketones differs in the performance of the amination of alcohols in that at least stoichiometric amounts of hydrogen must be present in the amination of aldehydes and ketones.
  • the pressure in the reaction vessel which results from the sum of the partial pressures of the aminating agent, the alcohol, aldehyde or ketone and the reaction products formed and optionally the solvent used at the indicated temperatures, is expediently increased by pressing on hydrogen to the desired reaction pressure ,
  • the catalyst is arranged as a fixed bed, it may be advantageous for the selectivity of the reaction to mix the shaped catalyst bodies in the reactor with inert fillers, so to speak to "dilute" them.
  • the proportion of the packing in such catalyst preparations may be 20 to 80, especially 30 to 60 and especially 40 to 50 parts by volume.
  • reaction water formed in the course of the reaction. per mole of reacted alcohol group, aldehyde group or keto group generally affects the degree of conversion, the reaction rate, the selectivity and the cat lysatorstandzeit not disturbing and is therefore expediently removed only during the workup of the reaction product from this, z. B. distillative.
  • the excess hydrogen and the optional excess amination agent are removed and the reaction crude product obtained is purified, e.g. by a fractional rectification. Suitable work-up procedures are e.g. in EP-A-1 312 600 and EP-A-1 312 599 ⁇ both BASF AG).
  • the excess aminating agent and the hydrogen are advantageously recycled back into the reaction zone. The same applies to the possibly not completely reacted alcohol, aldehyde or ketone component.
  • Unreacted starting materials and any appropriate by-products can be recycled back into the synthesis. Unreacted educts can be re-flowed through the catalyst bed in discontinuous or continuous operation after condensation of the products in the separator in the recycle gas stream.
  • Amination agents in the process according to the invention are, in addition to ammonia, primary and secondary amines.
  • R 1 , R 2 is hydrogen (H) 1 alkyl, such as d- ⁇ -alkyl, cycloalkyl, such as C 3 .
  • R 3 , R 4 is hydrogen (H), alkyl, such as C, _anAlkyl, Cycloalkyi, such as C 3 .
  • Hydroxyalkyf such as C 1 _ 2 o-hydroxy, amino noalkyi as C ⁇ o-aminoalkyl, hydroxyalkylaminoalkyl as C 2nd 2 o-hydroxyalkylaminoalkyl, alkoxyalkyl, such as C 2 _3- Alkoxyalkyl, Dialkyiaminoalkyl, such as C 3 _ 3 o-Dia kyla ⁇ ino- alkyl, Alkylamtnoalkyl, such as C 2 _3o-Alky aminoaikyl, R 5 -!
  • OCR 6 R 7 CR 8 RV OCR 6 R 7
  • aryl heteroaryl
  • Araikyi as C 7 _ 2 o-Araikyi
  • Heteroarylalkyf such as C ⁇ o-Heteroarylaikyl
  • alkylaryl such as C 7 _ 20 -Aikylaryl
  • Alkyfheteroaryl such as C ⁇ 20 -
  • Askylheteroaryl and Y- (CH 2 ) m -NR s - (CH 2 ) q or together - ⁇ CH 2 ) rX- (CH 2 ) m - or
  • R 5 , R 10 is hydrogen (H), alkyl, such as C 1-4 -alkyl, alkylphenyi, such as C 7- 40- alkylphenyl,
  • R 6 , R 7 , R 8 , R 9 is hydrogen (H), methyl or ethyl
  • X is CH 2 , CHR 5 , oxygen (O), sulfur (S) or NR 5 ,
  • n is an integer from 1 to 30 and
  • j, k, I, m, q is an integer from 1 to 4,
  • the process according to the invention is therefore preferably used for the preparation of an amine I application by reacting a primary or secondary alcohol of the formula II
  • the starting alcohol may also be an amino alcohol, e.g. an aminoalkanoi according to the formula Ii.
  • the reaction can also be carried out intramolecularly in a corresponding aminoalkohoi, aminoketone or amino aldehyde.
  • the process according to the invention is also preferably used in the preparation of a cyclic amine of the formula IV
  • R 11 and R 12 are hydrogen (H), alkyl, such as C 1 - to C 20 -alkyl, cycloalkyl, such as C 3 - to C 12 -
  • Z is CH 2 , CHR 5 , oxygen (O), NR 5 or NCH 2 CH 2 OH and
  • R 1 , R s , R 7 have the meanings given above,
  • Alkyl such as C 1-2 o -alkyl, preferably C 1-14 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, n-hexyl, iso-hexyl, sec-hexyl, cyclopentyimeth-yl, n-heptyl, iso-heptyi, cyclohexylmethyi, n Octyl, iso-octyl, 2-ethylhexyl, n-
  • Hydroxyalkyl such as d.ao hydroxyalkyl, preferably C 1-a hydroxyalkyl, more preferably C M hydroxyalkyl, such as hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxy-n-propyl, 2-hydroxy-n- propyl, 3-hydroxy-n-propyl! and 1-
  • Aminoalkyl as such as aminomethyl, 2-aminoethyl, 2-amino-1, 1-dimethylethyl, 2-amino-n-propyl, 3-amino-n-propyl, A-amino-n-butyl, 5-amino-n-pentyl, N - (2-aminoethyl) -2-aminoethyl and N- (2-
  • Hydroxyalkylaminoalky As C 2 . 20- hydroxyalkylaminoalkyl, preferably C 3-3 -hydroxyalkylaminoalkyl, such as (2-hydroxyethylamino) methyl, 2- (2- Hydroxyethyl amino) ethyl and 3- (2-hydroxyethylamino) propyl,
  • Alkylaminoaikyi such as C ⁇ o-Alkyiaminoalkyl, preferably C 2 . 2 % of alkylaminoalkyl, more preferably C 2 . 8- Alkylaminoalkyl, such as methylaminomethyl, 2-methylaminoethyl, ethylaminomethyl, 2-ethylaminoethyl! and 2- (isopropylmethyl) ethyl, (R 5 ) HN- (CH 2 ) q ,
  • Heteroarylalky like C 4 . 2 o-Heteroarylaiky [such as pyrid-2-yl-methyl, furan-2 ⁇ ymethyl, pyrro-3-yl-methyl and imidazol-2-yl-methyl,
  • Alkylheteroaryl such as C 4-2 o -atkyheteroaryl, such as 2-methyl-3-pyridinyl, 4,5-dimethylimidazol-2-yl, 3-methyl-2-furanyl and 5-methyl-2-pyrazinyl,
  • Heteroaryls such as 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, pyrazinyl, pyrrol-3-yl, imidazol-2-yl, 2-furanyl and 3-furanyl,
  • Cycloalkyl such as C 3 i 2 -cycloalkyl, preferably C 3 .e Cycloalky !, such as cyclopropyl, cyclo- dobutyl, cyclopentyl, cyclohexyl, cycloheptyl and Cyclooctyi, particularly preferably cyclopentyl and Cyclohexyi,
  • Alkoxyalkyf such as C 2-30 - Alkoxyalky I 1 preferably C 2 - 20 alkoxyalkyl, more preferably C 2-8 alkoxyalkyl, such as methoxymethyl, ethoxymethyl, n-Propoxymethyi, iso-Propoxymethyi, n-Butoxymethyi, iso-butoxymethyl, sec Butoxymethyl, tert-butoxymethyl, 1-methoxyethyl and 2-methoxyethyl, more preferably C 2-4
  • Dialkylaminoatkyi such as C 3 . 30 -dialkylaminoalkyl, preferably C 3-2 o -dialkylaminoalkyl, more preferably C 3, 10-dioxylaminoalkyl, such as N, N-dimethylaminomethyl, (N, N-dibutylamino) methyl, 2- ⁇ N, N-dimethylamino) ethyl , 2- ⁇ N, N-
  • Aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-aminotryl, 2-anthryl and 9-anthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, more preferably phenyl,
  • Alkylaryl such as C 7-2 o -alkylaryl, preferably C 7-12 -alkylphenylene, such as 2-methylphenyi, 3-methylphenol, 4-methylphenyl, 2,4-dimethylphenyi, 2,5-dimethylphenyi, 2,6 Dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,3,4-trimethylphenyl, 2,3,5-trimethylphenol, 2,3,6-trimethylphenyl, 2,4,6-trmethylphenyi, 2- Ethylphenyi, 3-ethylphenyi, 4-ethylphenyl, 2-n-propylpheny! t is 3- ⁇ -propylphenyl and 4-n-propylphenyl;
  • Aralkyl such as C 7-2 o-aralkyl, preferably C 7 .i 2 -phenyiaikyl, such as benzyl, p-methoxybenzyl, 3,4-dirnethoxybenzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2- Propyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-
  • R 3 and R 4 or R 2 and R 4 together form a - (CH 2 ) 1 -X- (CH 2 ) 1, - group, such as - (CH 2 ) 3 -, - (CH 2 ) 4 -, - (CHz) 5 -, - (CH 2 J 6 -, - (CH 2 ) 7 -, - (CH 2 ) -O- (CH 2 ) 2 -, - (CH 2 ) -NR S -
  • R 1 , R 2 - alkyl, such as Ci. 20- alkyl, preferably Ci -8- alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl , sec-pentyl, ⁇ -e-pentyl, 1,2-dimethylpropyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, 2-ethylhexyl, especially preferably Cu-alkyl, or
  • R 1 and R 2 together form a - (CH 2 ) r X- (CH 2 ) k - group, such as - (CH 2 ) 3 -, - (CH 2 J 4 -, - (CH 2 ) S -, - (CH 2 Je-, - (CH 2 J 7 -, - (CH 2 ) -O- (CHz) r, - (CH 2 ) -NR 5 - (CH 2 ) 2 -, - (CH 2 J-CHR 5 - (CH 2 J 2 -, - (CH 2 J 2 -O- (CH 2 J 2 -, - (CH 2 ) 2 -NR 5 - (CH 2 ) 2 -, - (CH 2 ) 2 -CHR 5 - (CH 2 J 2 -, -CH 2 -O- (CHa) 3 -, -CH 2 -NR 5 - (CH 2 ) 3 -, -CH 2 -CHR 5
  • Alkyl preferably C 1-4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, preferably methyl and ethyl, especially preferred added methyl,
  • Alkylphenyl preferred such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2, 3, 4-nonylphenyl, 2-, 3-, 4-decylphenyi,
  • R 6 , R 7 , R 8 , R 9 methyl or ethyl, preferably methyl
  • Alkyl such as C 1 - to C 20 -alkyl, cycloalkyl, such as C 3 - to C 12 -cycloalkyl, aryl, heteroaryl, aralkyl, such as C 7 - to C 20 -arabyl, and alkylaryl, such as C 7 - to C 20 -alkylaryl, each as defined above,
  • C 2-2 o-alkylaminoalkyl preferably C 2 -alkyl- ⁇ -aminoalkyl, such as methylaminomethyl, 2-methylaminoethyl, ethylaminomethyl, 2-ethylaminoethyl and 2- (iso-propylamino) ethyl,
  • C 3 . 2 o-dialkyiaminoalkyl preferably C 3 . 16 -dialkylaminoalkyl such as dimethylamino-methyl, 2-dimethylaminoethyl, 2-diethylaminoethyl, 2- (di-n-propylamino) ethyl and 2- (diisopropylamino) ethyl,
  • k, m, q an integer from 1 to 4 ⁇ 1, 2, 3 or 4), preferably 2, 3 and 4, more preferably 2 and 3,
  • n an integer from 1 to 30, preferably a whole number! from 1 to 8 (1, 2, 3, 4, 5, 6, 7 or 8), more preferably an integer from 1 to 6.
  • alcohols are suitable among the o.g. Prerequisites virtually all primary and secondary alcohols with aliphatic OH function.
  • the alcohols can be straight-chain, branched or cyclic. Secondary alcohols are aminated as well as primary alcohols.
  • the alcohols may also bear substituents or contain functional groups which are inert under the conditions of the hydrogenating amination, for example alkoxy, alkenyloxy, alkylamino or dialkylamino groups, or else optionally hydrogenated under the conditions of the hydrogenating amination, for example CC double - or triple bonds.
  • polyhydric alcohols are to be aminated, it is possible to obtain control of the reaction conditions in hand, preferably amino alcohols, cyclic amines or multiply aminated products.
  • 1,6-dioxene leads depending on the choice of reaction conditions to 1-amino-6-hydroxy, 1, 6-diamino Verbsnditch or seven-membered rings with a nitrogen atom (Hexamethyle ⁇ imine).
  • alcohols are preferably aminated:
  • Diethylamino-pentanol-4 ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diglycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediof, 2,2-bis [4 -hydroxycyclohexyl] propane, methoxyethanol, propoxyethanol, butoxyethanol, polyisobutyl alcohols, polypropylic alcohols, polyethylene glycol ethers, polypropylene glycol ethers and polybutylene glycol ethers.
  • the latter polyalkylene glycol ethers are converted in the inventive reaction by conversion of their free hydroxyl groups to the corresponding amines.
  • Particularly preferred alcohols are methanol, ethanoS, n-propanol, i-propanol, n-butanoi, sec-butanol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-ethylhexanol, cyclohexanol, fatty alcohols , Ethylene glycol, diethylene glycol (DEG), triethylene glycol (TEG), 2- (2-dimethylamino-ethoxy) ethanol, N-methyldiethanolamine and 2- (2-dimethylaminoethoxy) ethanol.
  • DEG diethylene glycol
  • TEG triethylene glycol
  • 2- (2-dimethylamino-ethoxy) ethanol N-methyldiethanolamine
  • 2- (2-dimethylaminoethoxy) ethanol 2- (2-dimethylaminoethoxy
  • ketones which can be used in the process according to the invention practically all aliphatic and aromatic ketones are suitable under the abovementioned conditions.
  • the aliphatic ketones may be straight-chained, branched or cyclic, which may be ketones Contain heteroatoms.
  • the ketones may also carry substituents or contain functional groups which are inert under the conditions of the hydrogenating amination, for example alkoxy, Aikenyioxy-, alkylamino or Dialkytami- no phenomenon, or else optionally hydrogenated under the conditions of the hydrogenating amination be CC double or triple bonds. If multivalent ketones are to be aminated, it is possible to obtain control of the reaction conditions by hand, aminoketones, amino alcohols, cyclic amines or multiply aminated products.
  • ketones are preferably hydrogenated aminatively:
  • Suitable aldehydes for use in the process according to the invention are suitable among the above-mentioned. Prerequisites virtually all aliphatic and aromatic aldehydes.
  • the aliphatic aldehydes may be straight-chain, branched or cyclic, the aldehydes may contain heteroatoms.
  • the aldehydes may further bear substituents or contain functional groups which are inert under the conditions of the hydrogenating amination, for example alkoxy, Aikenyioxy-, alkylamino or dialkyiamino phenomenon, or else optionally hydrogenated under the conditions of the hydrogenating amination, for example CC -Double or triple bonds. If polyfunctional aldehydes or keto aldehydes are to be aminated, it is possible to obtain them by controlling the reaction conditions in the hand, aminoacids, cyclic amines or multiply aminated products.
  • aldehydes are preferably hydrogenated aminatively:
  • both ammonia and primary or secondary, aliphatic or cycloaliphatic or aromatic amines can be used.
  • the alcoholic hydroxyl group or the aldehyde group or the keto group is first converted into the primary amino groups (-NH 2 ).
  • the primary amine formed in this way can react with further alcohol or aldehyde or ketone to form the corresponding secondary amine, which in turn reacts with further alcohol or aldehyde or ketone to form the corresponding, preferably symmetrical, tertiary amine.
  • primary, secondary or tertiary amines can be prepared in this manner as desired.
  • cyclic amines such as e.g. Pyrrolidines, piperidines, hexamethylenimines, piperazines and morpho-acids.
  • primary or secondary amines can be used as aminating agents! use.
  • aminating agents are preferably used for the preparation of unsymmetrically substituted di- or trialkylamines, such as ethyldiisopropylamine and ethyldicyclohexylamine.
  • di- or trialkylamines such as ethyldiisopropylamine and ethyldicyclohexylamine.
  • mono- and dialkylamines are used as aminating agents: monomethylamine, dimethylamine, monoethylamine, diethylamine, n-propylamine, di-n-propylamine, iso-propylamine, diisopropylamine, isopropylethylamine, n-butyl!
  • amine di-n-butylamine, s-butylamine, di-s-butylamine, iso-butylamine, n-pentylamine, s-penty! amine, iso-pentylamine, n-hexy! amine, s-hexy! arnine, iso-hexy! amine, cyclohexyamine, aniline, toluidine, piperidine, morpholine and pyrrolidine.
  • Amines particularly preferably prepared by the process according to the invention are, for example, morpholine (from aminodiglycol), morpholine and / or 2,2'-dimorpholino-diethyl ether (DMDEE) (from DEG and ammonia), 6-dimethylthiohexanol-1 (from hexanediol and dimethylamine (DMA)), triethylamine (from of ethanol and diethylamine (DEA)), Dimethylethylamtn (out of ethanol and DMA), N- (Ci.
  • morpholine from aminodiglycol
  • morpholine and / or 2,2'-dimorpholino-diethyl ether (DMDEE) from DEG and ammonia
  • 6-dimethylthiohexanol-1 from hexanediol and dimethylamine (DMA)
  • triethylamine from of ethanol and diethylamine (DEA)
  • kyi) amine for example N, N-dimethyl-N-cyclohexylamine (DMCHA), Poiyisobutenamin (from Pib-oxo and NH 3), N, N-diisopropyl- N-ethylamine ( Hünig base) (from N, N-diisopropylamine and acetaldehyde), N-methyl-N-isopropylamine (MMSPA) (from monomethylamine and acetone), n-propylamines (such as mono- / di-n-propylamine, N, N-dimethyl- Nn-propylamine (DMPA)) (from propionaldehyde and / or n-propanol and NH 3 or DMA), N, N-dimethyl-N-isopropylamine (DMIPA) (from i-propanoi and / or acetone and DMA), N , N-dimethyl-N-butylamine (1-, 2-
  • the respective pure products can be obtained from the hydrous raw materials by rectification under vacuum, atmospheric pressure or elevated pressure according to the known methods.
  • the pure products fall either directly in pure form or as an azeotrope with water.
  • Water-containing azeotropes can be dehydrated by means of a liquid-liquid extraction with concentrated sodium hydroxide solution before or after the purifying distillation.
  • a distillative dewatering in the presence of a Schleppmitteis by ⁇ known methods is also possible.
  • a dehydration by a separation of the organic and the aqueous phase by known methods is also possible.

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

Abstract

Procédé de production en continu d'une amine par mise en réaction d'un alcool primaire ou secondaire, d'un aldéhyde et / ou d'une cétone avec de l'hydrogène et un composé d'azote choisi dans le groupe constitué par ammoniac et des amines primaires et secondaires, à une température de l'ordre de 80 à 350 °C en présence d'un catalyseur contenant du dioxyde de zirconium, la masse catalytiquement active du catalyseur avant sa réduction avec l'hydrogène étant composée de 90 à 99,8 % en poids de dioxyde de zirconium (ZrO<SUB>2</SUB>), de 0,1 à 5,0 % en poids de composés oxygénés du palladium et de 0,1 à 5,0 % en poids de composés oxygénés du platine.
PCT/EP2006/063384 2005-06-23 2006-06-21 Procede de production en continu d'une amine Ceased WO2006136571A1 (fr)

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DE102005029093A DE102005029093A1 (de) 2005-06-23 2005-06-23 Verfahren zur kontinuierlichen Herstellung eines Amins
DE102005029093.0 2005-06-23

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Cited By (9)

* Cited by examiner, † Cited by third party
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CN101973963A (zh) * 2010-09-26 2011-02-16 安徽华业化工有限公司 以吗啉高沸物为原料合成2,2-二吗啉基二乙基醚的方法
CN102070461A (zh) * 2010-12-07 2011-05-25 浙江新化化工股份有限公司 N-甲基异丙胺的合成方法
CN102617355A (zh) * 2011-01-26 2012-08-01 中国科学院大连化学物理研究所 一种经由伯胺脱氨制备仲胺的方法
CN105992754A (zh) * 2014-02-18 2016-10-05 巴斯夫欧洲公司 制备n-乙基二异丙胺的方法
CN106478423A (zh) * 2016-10-09 2017-03-08 杭州新德环保科技有限公司 合成n,n‑二异丙基乙胺的方法
CN106588672A (zh) * 2016-12-31 2017-04-26 浙江建业化工股份有限公司 二异丙基乙胺的生产方法
CN106866424A (zh) * 2017-03-03 2017-06-20 常州沃腾化工科技有限公司 N‑甲基异丙胺的间歇式制备方法
CN110713469A (zh) * 2019-09-26 2020-01-21 宿州亿帆药业有限公司 一种十三吗啉的合成工艺
CN117209443A (zh) * 2023-07-31 2023-12-12 合肥远志医药科技开发有限公司 一种4-环十二烷基-2,6-二甲基吗啉的制备方法

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CN109608340A (zh) * 2018-12-18 2019-04-12 江苏万盛大伟化学有限公司 N，n-二甲基环己胺的制备方法

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US20010003136A1 (en) * 1999-12-06 2001-06-07 Jan Nouwen Process for preparing amines
US20040122259A1 (en) * 2002-12-20 2004-06-24 Till Gerlach Preparation of an amine
WO2005110969A1 (fr) * 2004-05-13 2005-11-24 Basf Aktiengesellschaft Procede de production en continu d'une amine

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EP0143271A1 (fr) * 1983-10-26 1985-06-05 Abbott Laboratories Sels acides d'acide valproique
EP0701995A2 (fr) * 1994-08-16 1996-03-20 Basf Aktiengesellschaft Procédé de préparation d'amines aromatiques à partir d'amines aliphatiques et leur préparation par hydrogénation en présence d'amines
US6111141A (en) * 1999-01-14 2000-08-29 Basf Aktiengesellschaft Preparation of N-ethyldiisopropylamine
US20010003136A1 (en) * 1999-12-06 2001-06-07 Jan Nouwen Process for preparing amines
US20040122259A1 (en) * 2002-12-20 2004-06-24 Till Gerlach Preparation of an amine
WO2005110969A1 (fr) * 2004-05-13 2005-11-24 Basf Aktiengesellschaft Procede de production en continu d'une amine

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101973963A (zh) * 2010-09-26 2011-02-16 安徽华业化工有限公司 以吗啉高沸物为原料合成2,2-二吗啉基二乙基醚的方法
CN102070461A (zh) * 2010-12-07 2011-05-25 浙江新化化工股份有限公司 N-甲基异丙胺的合成方法
CN102617355A (zh) * 2011-01-26 2012-08-01 中国科学院大连化学物理研究所 一种经由伯胺脱氨制备仲胺的方法
CN102617355B (zh) * 2011-01-26 2013-11-20 中国科学院大连化学物理研究所 一种经由伯胺脱氨制备仲胺的方法
CN105992754A (zh) * 2014-02-18 2016-10-05 巴斯夫欧洲公司 制备n-乙基二异丙胺的方法
CN106478423A (zh) * 2016-10-09 2017-03-08 杭州新德环保科技有限公司 合成n,n‑二异丙基乙胺的方法
CN106588672A (zh) * 2016-12-31 2017-04-26 浙江建业化工股份有限公司 二异丙基乙胺的生产方法
CN106588672B (zh) * 2016-12-31 2019-02-22 浙江建业化工股份有限公司 二异丙基乙胺的生产方法
CN106866424A (zh) * 2017-03-03 2017-06-20 常州沃腾化工科技有限公司 N‑甲基异丙胺的间歇式制备方法
CN110713469A (zh) * 2019-09-26 2020-01-21 宿州亿帆药业有限公司 一种十三吗啉的合成工艺
CN117209443A (zh) * 2023-07-31 2023-12-12 合肥远志医药科技开发有限公司 一种4-环十二烷基-2,6-二甲基吗啉的制备方法

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