Classifications

• • 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
  • C07D295/023—Preparation; Separation; Stabilisation; Use of additives
• • 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

Definitions

• the present invention relates to a process for preparing an amine by reacting an aldehyde and / or ketone with hydrogen and a nitrogen compound selected from the group of primary and secondary amines in the presence of a heterogeneous catalyst.
• the process products find inter alia. Use as intermediates in the preparation of fuel additives (US-A-3,275,554, DE-A-21 25 039 and DE-A-36 11 230), surfactants, drugs and crop protection agents, hardeners for epoxy resins, catalysts for polyurethanes, intermediates for the preparation quaternary ammonium compounds, plasticizers, corrosion inhibitors, synthetic resins, ion exchangers, textile auxiliaries, dyes, vulcanization accelerators and / or emulsifiers.
• fuel additives US-A-3,275,554, DE-A-21 25 039 and DE-A-36 11 230
• surfactants drugs and crop protection agents
• hardeners for epoxy resins catalysts for polyurethanes
• intermediates for the preparation quaternary ammonium compounds plasticizers
• corrosion inhibitors synthetic resins
• ion exchangers textile auxiliaries
• dyes dyes
• vulcanization accelerators and / or emulsifiers emuls
• EP-A-611 137 (Sumitomo Chem. Comp.) Relates to the reductive amination of cyclic ketones, wherein in a first stage a corresponding imino compound is prepared, which is subsequently hydrogenated.
• EP-A2-312 253 (Kao Corp.) describes the use of specific copper catalysts in the preparation of N-substituted amines from alcohols or aldehydes.
• EP-A1-827 944 (BASF AG) relates to the use of thin film catalysts in processes for the hydrogenation of polyunsaturated C2- ⁇ -hydrocarbons.
• DE-A1-101 56 813 (BASF AG) describes a process for the selective synthesis of polyalkyleneamines using phosphorus-containing thin-film catalysts.
• US-A1-2003 / 0049185 (Air Products) describes an improved reactor with a monolith catalyst and its use in oxidations and hydrogenations, especially of nitro compounds.
• EP-A1-1 358 935 (Air Products) relates to supported Ni catalysts with Pd as promoter and a metal selected from Zn, Cd, Cu and Ag as promoter. Monolithic support materials are mentioned optionally.
• the catalysts are used in the amination of alcohols and in the hydrogenation of nitro compounds.
• WO-A-99/32529 (Shell) teaches a process for the hydrogenation of macromolecular organic substrates in the presence of a catalyst having a megapore structure.
• the process should include a catalyst of high activity and selectivity (comparable to a suspension catalyst) characterized by easy separability from the reaction mixture (analogous to a fixed bed catalyst).
• a process for the preparation of an amine has been found by reacting an aldehyde and / or ketone with hydrogen and a nitrogen compound selected from the group of primary and secondary amines in the presence of a heterogeneous catalyst which is characterized in that the catalyst is a Kataiysatorpackung is that can be produced by applying at least one catalytically active metal and / or at least one compound of this metal to a fabric, a knitted fabric or a film as a carrier material.
• the catalysts used according to the invention have the structure described below.
• a variety of films and fabrics, as well as knitted fabrics, such as knitted fabrics can be used. It can be used according to the invention tissues with different weave, such as smooth tissue, twill, Tressengewebe, Jardinschaft- Atlas fabric or other special weave fabrics.
• tissue made of weavable metal wires such as iron, spring steel, brass, phosphor bronze, pure nickel, monel, aluminum, silver, nickel silver, nickel, chrome nickel, chromium steel, stainless, acid-resistant and highly heat-resistant chromium nickel steels and titanium into consideration. The same applies to knitted fabrics, eg knitted fabrics.
• woven or knitted fabrics of inorganic materials such as Al 2 O 3 and / or SiO 2 may be used.
• Synthetic wires and fabrics made of plastics can also be used according to an embodiment of the invention.
• plastics can also be used according to an embodiment of the invention.
• examples are polyamides, polyesters, polyvinyls, polyolefins, such as polyethylene, polypropylene, polytetrafluoroethylene, and other plastics that can be processed into woven or knitted fabrics.
• Preferred support materials are metal foils or metal mesh, such as stainless steels with the material numbers 1.4767, 1.4401, 2.4610, 1.4765, 1.4847, 1.4301, etc.
• the designation of these materials with the mentioned material numbers follows the information of the material numbers in the "Stahleisenliste", published by the Association of German Iron and Steelmen , 8th edition, pages 87, 89 and 106, Verlag Stahleisen mbH, Dusseldorf, 1990.
• the material of the material number 1.4767 is also known under the name Kanthai.
• the metal foils and metal meshes are particularly well suited because they can be roughened by means of tempering at the surface before coating with catalytic active compounds or promoters.
• the metallic support at temperatures of 400 to 1100 0 C, preferably 800 to 1000 0 C, for 0.5 to 24 hours, preferably 1 to 10 hours, heated in an oxygen-containing atmosphere, such as air.
• the activity of the catalyst can be controlled or increased.
• the catalyst supports used according to the invention can be coated according to the invention by means of different processes with catalytically active compounds and promoters.
• the application of the catalyst and / or promoter active substances by impregnation of the carrier in the substance (eg according to EP-A1-965 384 (BASF AG)), by electrochemical deposition or deposition in the presence of a reducing agent (electroless deposition).
• the catalyst web or catalyst sheet may then be formed into monoliths for incorporation into the reactor in accordance with one embodiment of the invention.
• the deformation can also take place before the application of the active substances or promoters.
• the catalyst supports which can be used according to the invention can be coated with "thin layers" of catalytically active compounds and promoters by means of a vacuum evaporation technique.
• "thin layers” denominations in the thickness range between a few ⁇ (1O 10 m) and a maximum of 0.5 microns are called.
• vacuum evaporation techniques various methods can be used in the present invention. Examples are thermal evaporation, flash evaporation, sputtering and the combination of thermal evaporation and sputtering. The thermal evaporation can be done by direct or indirect electrical heating.
• An evaporation by means of electron beam can also be used according to the invention.
• the substance to be evaporated is superficially heated in a water-cooled crucible with an electron beam so that even refractory metals and dielectrics are vaporized.
• suitable amounts of reactive gases to the residual gas chemical reactions can be effected according to an embodiment of the invention during layering by vapor deposition techniques.
• suitable reaction can thus oxides, nitrides or carbides are produced on the support.
• the carriers in particular the woven fabrics, knitted fabrics and films, can be steamed discontinuously or continuously in a vacuum vapor deposition unit.
• a vacuum vapor deposition unit For example, carried out the vapor deposition by heating the catalytically active component or compound, such as a precious is tall so strongly heated in vacuo at 10 "2 to 10" 10 Torr, preferably from 10 "4 to 10 8 Torr by an electron beam,
• the carrier fabric or knits are expediently arranged in such a way that the largest possible part of the vapor stream condenses on the carrier, whereby the woven or knitted fabrics can be continuously fed by means of a built-in winding machine
• continuous sputtering in an air-to-air system is preferred.
• EP-A2-198 435 discloses the production of a catalyst net packet by vapor deposition of stainless steel mesh with platinum or platinum and rhodium.
• one or more catalytically active compounds or promoters can be vapor-deposited.
• the coatings with catalytically active substance are preferably in the thickness range from 0.2 nm to 100 nm, more preferably 0.5 nm to 20 nm, in particular 3 nm to 7 nm.
• the elements of sub-group VIII of the Periodic Table of the Elements are used as catalytically active compounds, preferably nickel, palladium and / or platinum, in particular palladium.
• Promoters can be present according to an embodiment of the invention and according to the invention for example be selected from the elements of III., IV., V., VI. Main group and the I., II., III., VI., VII. Subgroup of the Periodic Table of the Elements (Chemical Abstracts Service group notation).
• the promoter used according to one embodiment of the invention is preferably selected from copper, silver, gold, zinc, chromium, cadmium, lead, bismuth, tin, antimony, indium, gallium, germanium, tungsten or mixtures thereof preferably silver, indium and germanium, copper, gold, zinc, chromium, cadmium, lead, bismuth, tin, antimony.
• the layer thickness of at least one promoter used according to an embodiment of the invention is 0.1 to 20 nm, preferably 0.1 to 10 nm, in particular 0.5 to 3 nm.
• the carrier Before applying the catalytically active substance and / or the promoter, the carrier can be modified by vapor deposition of a layer of an oxidizable metal and subsequent oxidation to form an oxide layer.
• the oxidizable metal used is magnesium, aluminum, silicon, titanium, zirconium, tin or germanium, as well as mixtures thereof.
• the Thickness of such an oxide layer is according to the invention preferably in the range of 0.5 to 200 nm, preferably 0.5 to 50 nm.
• the precoat support material can be tempered after the coating, game, a palladium-coated carrier material examples at temperatures ranging from 200 to 800 0 C, preferably 300 to 700 0 C, for example 0.5 to 2 hours.
• the catalyst can, if desired or necessary, with hydrogen at temperatures of 20 to 25O 0 C, preferably 100 re- pokerd to 200 0 C. This reduction can also preferably be carried out in the reactor itself.
• the catalysts can be constructed systematically, for example in an evaporator with several different evaporation sources.
• an oxide layer or, by reactive evaporation, an adhesive layer may first be applied to the substrate.
• catalytically active components and promoters can be vaporized in several alternating layers.
• promoter layers of oxides and other compounds can be produced. Tempering steps can also be interposed or followed.
• the application of the at least one active substance as a catalyst and / or promoter can also be effected by impregnation.
• the catalysts produced by vapor deposition according to the invention in particular catalyst webs, catalyst knits and catalyst foils have a very good adhesive strength of the catalytically active compounds or promoters. Therefore, they can be deformed, cut and processed, for example, into monolithic catalyst elements, without the catalytic active compounds or promoters detaching.
• catalyst fabrics, catalyst knits and catalyst films according to the invention it is possible to produce any desired shaped catalyst packings for a reactor, for example a flow-through reactor, a reaction column or distillation column. It is possible to produce catalyst packing elements with different geometries, as known from the distillation and extraction technology.
• Examples of advantageous catalyst packing geometries according to the invention which offer the advantage of low pressure loss in operation are Montz A 3 and Sulzer BX, DX and EX types.
• An example of a catalyst geometry of catalyst foils or catalyst expanded metal foils according to the invention are those of the Montz BSH type.
• the amount of catalyst processed per unit volume, in particular amount of catalyst tissue, amount of catalyst or catalyst film can be controlled in a wide range, resulting in a different size of the openings or channel widths in the catalyst fabric, catalyst knit or in the Katalysatorfo- lie.
• By appropriate selection of the amount of catalyst fabric, catalyst knit or catalyst film per unit volume of the maximum pressure drop in the reactor, such as flow or distillation reactor can be adjusted, and thus the catalyst can be adapted to experimental specifications.
• the catalyst used according to the invention preferably has a monolithic form, as described, for example, in EP-A2-564 830. Further suitable catalysts are described in EP-A1-218 124 and EP-A1-412 415.
• Another advantage of the monolithic catalysts used according to the invention is the good fixability in the reactor bed, so that they can be used very well for example in hydrogenation in the liquid phase in the upflow mode at high cross-sectional loading.
• the catalyst pack In gas phase hydrogenation, the catalyst pack is resistant to shock or vibration. There is no abrasion.
• the catalysts described above are used according to the invention in a process for preparing an amine by reacting an aldehyde and / or ketone with hydrogen and a nitrogen compound selected from the group of primary and secondary amines.
• these aldehydes and ketones can be converted into the corresponding secondary and tertiary amines with high selectivity and high yield.
• the amination of the carbonyl compound is preferably carried out in the liquid phase, preferably in two reactors connected in series, wherein in the first reactor a conversion of 60 to 99% is achieved. In the second reactor, the residual conversion is achieved, or it serves as a safety reactor.
• an adiabatically operated reactor with or without recycle may be sufficient.
• the amination is carried out in a preferred embodiment in a backmixed isothermal reactor and a connected adiabatic reactor.
• the reaction is carried out in the liquid phase or in a mixed liquid / gas phase with at least 50% by weight of the reaction mixture in the liquid phase.
• the amination can be carried out according to an embodiment of the invention in the trickle way or in the upflow mode.
• the added hydrogenating hydrogen can be present dissolved in the liquid phase.
• reactors e.g. Tubular reactors are used.
• the inlet temperature of the educt mixture in the amination is according to one embodiment of the invention -10 to 150 c C, preferably 0 to 120 0 C, in particular 0 to 90 0 C.
• suitable temperature and pressure parameters in the o.g. Areas are selected, which depends on the particular mixture used.
• the nitrogen compound is preferably used 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 aldehyde and / or ketone.
• the process according to the invention is preferably carried out at an absolute pressure in the range from 1 to 300 bar, preferably 1 to 100 bar, more preferably 1 to 50 bar, particularly preferably 1 to 30 bar.
• the inventive method of aldehyde and / or Ketonaminierung is preferably carried out at a temperature in the range of 60 to 200 0 C, preferably 80 to 170 0 C, particularly preferably 100 to 150 ° C.
• an amount of exhaust gas from 5 to 800 standard cubic meters / h, in particular 20 to 300 standard cubic meters / h, driven.
• the catalyst loading is preferably in the range of 0.1 to 2.0, preferably 0.1 to 1.0, particularly preferably 0.2 to 0.6, kg of aldehyde and / or ketone per liter of catalyst (bulk volume) and hour.
• the pressure in the reactor which is the sum of the Partial pressures of the aminating agent, the aldehyde and / or ketone component and the reaction products formed at the indicated temperatures, is advantageously increased by pressing hydrogen to the desired reaction pressure.
• reaction water formed in the course of the reaction generally does not interfere with the degree of conversion, the reaction rate, the selectivity and the catalyst life and is therefore expediently removed from the reaction product only during the work-up of the reaction product, e.g. by distillation.
• reaction effluent From the reaction effluent, after it has been expediently expanded, the excess hydrogen and the excess amination agent optionally present 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).
• Unreacted starting materials and any appropriate by-products can be recycled back into the synthesis. Unreacted starting materials can be re-flowed over the catalyst bed in discontinuous or continuous operation after condensation of the products in the separator in the circulating gas stream.
• R 1, R 2 is hydrogen (H), alkyl, such as Ci -2 o alkyl, cycloalkyl such as C 3 -
• R 3 is hydrogen (H), alkyl, such as Ci-20 alkyl, cycloalkyl, such as C 3-12 cycloalkyl, hydroxyalkyl, such as 2 CI_ o-hydroxyalkyl, aminoalkyl, such as Ci-20 aminoalkyl, hydroxyalkylaminoalkyl as C2-20- hydroxyalkylaminoalkyl, alkoxyalkyl such as C2-30- alkoxyalkyl, dialkylaminoalkyl, such as C3-3o-dialkylaminoalkyl, alkylaminoalkyl, such as C 2 - 3 o-alkylaminoalkyl, R 5 - (OCR 6 R 7 CR 8 RV (OCR 6 R 7 ), aryl, heteroaryl, aralkyl, such as C 7-2o aralkyl, heteroarylalkyl, such as C 1-8 heteroarylalkyl, alkylaryl, such as C 7-30 alkylaryl, alkyl
• R 2 and R 4 together are - (CH 2) iX (CH 2) m-,
• R 5 , R 10 are hydrogen (H), alkyl, such as C 1-4 -alkyl, alkylphenyl, such as C 7-4 -alkyl-phenyl,
• R 6 , R 7 , R ⁇ , R 9 is hydrogen (H), methyl or ethyl
• X is CH 2 , CHR 5 , oxygen (O), sulfur (S) or NR 5 ,
• 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 by reacting an aldehyde and / or a ketone of the formula VI or VII
• the reaction can also be carried out intramolecularly in a corresponding amino ketone or aminoaldehyde.
• the radical R 4 (R 3 ) CH- is therefore formally replaced by a hydrogen atom of the nitrogen compound IM by the radical R 4 (R 3 ) CH- with the release of one molar equivalent of water.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 - hydrogen (H), (R 1 and R 2 are not both simultaneously H),
• Alkyl such as C 2 o alkyl, preferably C 1 -C 4 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n -Pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, n-hexyl, iso-hexyl, sec-hexyl, cyclopentylmethyl, n-heptyl, iso-heptyl, cyclohexylmethyl, n Octyl, isooctyl, 2-ethylhexyl, n-decyl, 2-n-propyl-n-heptyl, n-tridecyl, 2-n-butyl-n-nonyl and 3-n-butyl-n-n
• Hydroxyalkyl such as C 2 o-hydroxyalkyl, preferably Ci-s-hydroxyalkyl, more preferably Ci-4-hydroxyalkyl, such as hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl,
• Aminoalkyl such as Ci-2o-aminoalkyl, preferably d- ⁇ -aminoalkyl, such as aminomethyl, 2-aminoethyl, 2-amino-1,1-dimethylethyl, 2-amino-n-propyl, 3-amino-n-propyl, A -
• Hydroxyalkylaminoalkyl such as C2-2o-hydroxyalkylaminoalkyl, preferably C3-8-hydroxyalkylaminoalkyl, such as (2-hydroxyethylamino) methyl, 2- (2-hydroxyethylamino) ethyl and 3- (2-hydroxyethylamino) propyl,
• Alkylaminoalkyl such as C2-3o-alkylaminoalkyl, preferably C 2 - 2 o-alkylaminoalkyl, particularly preferably C ⁇ - ⁇ -alkylaminoalkyl, such as methylaminomethyl, 2-methyl-aminoethyl, ethylaminomethyl, 2-ethylaminoethyl and 2- (iso-propylamino) ethyl , (R 5 ) HN- (CH 2 ) q ,
• Heteroarylalkyl such as C4-2-o heteroarylalkyl, such as pyrid-2-yl-methyl, furan-2-ylmethyl, pyrrol-3-yl-methyl, and imidazol-2-yl-methyl,
• Alkyl heteroaryl such as C 4 .
• 2- o-alkylheteroaryl 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 C3 1 2-cycloalkyl, preferably C3-8 cycloalkyl such as Cydopropyl, Cy clobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, particularly preferably cyclopentyl and cyclohexyl,
• Alkoxyalkyl such as C2-3o-alkoxyalkyl, preferably C2-2o-alkoxyalkyl, particularly preferably C2- ⁇ -alkoxyalkyl, such as methoxymethyl, ethoxymethyl, n-propoxymethyl, iso-propoxymethyl, n-butoxymethyl, iso-butoxymethyl, sec-butoxymethyl , tert-butoxymethyl, 1-methoxyethyl and 2-methoxyethyl, more preferably Ca -4 -alkoxyalkyl,
• Dialkyiaminoalkyl such as C3-3o-dialkylaminoalkyl, preferably C3-2o-dialkylaminoalkyl, more preferably C3-io-dialkylaminoalkyl, such as N, N-dimethylaminomethyl, (N, N-dibutylamino) methyl, 2- (N, N-dimethylamino) ethyl , 2- (N, N-Diethylamino) ethyl, 2- (N, N-dibutylamino) ethyl, 2- (N, N-di-n-propylamino) ethyl and 2- (N, N-diiso -propylamino) ethyl, 3- (N, N-dimethylamino) propyl, (R 5 ) 2 N- (CH 2 ) q ,
• Aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl and 9-anthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, more preferably phenyl,
• alkylaryl such as C 7- 2o-alkylaryl, preferably C 7-i2-alkylphenyl, such as 2-methylphenyl, 3- methylphenyl, 4-methylphenyl, 2,4-Dimethyiphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2-n-propylphenyl, 3-n-propylphenyl and 4-n-propylphenyl,
• Aralkyl such as C 7- 20 aralkyl, preferably C 7-i2-Phenyialkyl such as benzyl, p-methoxy benzyl, 3,4-dimethoxybenzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl , 3-phenyl-propyl, 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, more preferably benzyl, 1-phenethyl and 2-phenethyl, R 3 and R 4 or R 2 and R 4 together form a - (CH 2 ) 1 -X- (CH 2 ) m group, such as - (CHz) 3 -, - (CHz) 4 -, - (CHz) 5 - , - (CHz) 6 -, - (CHz) 7 -, - (CHz) -
• Alkyl such as Ci -2 o alkyl, preferably Ci- 8 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n- Pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, 2-ethylhexyl, more preferably Ci -4 alkyl, or
• R 1 and R 2 together form a - (CH2) Jx (CHz) ⁇ ⁇ - group, such as - (CH 2) 3 -, - (CH 2) 4 -, - (CH 2) S-, - (CH 2 ) B, - (CHz) 7 -, - (CHz) -O- (CHz) 2 -, - (CH 2 ) -NR S - (CH 2 ) z -, - (CHz) -CHR S - ( CHz) 2 -, - (CH 2) 2 -O- (CH 2) 2 -, - (CH 2) 2 -NR 5 - (CH 2) 2 -, - (CH 2) z-CHR 5 - (CH 2 ) z, -CH 2 -O- (CHz) 3 -, -CHz-NR 5 - (CHz) 3 -, -CHz-NR 5 - (CHz) 3 -, -CHz-NR 5 - (CH
• Alkyl preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, preferably methyl and ethyl, more preferably 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-decylphenyl, 2,3-, 2,4-, 2,5-, 3,4-, 3,5-dinonylphenyl, 2,3-, 2,4-, 2 , 5-, 3,4- and 3,5-didecylphenyl, especially C ⁇ -zo-alkylphenyl,
• Methyl or ethyl preferably methyl
• N (R 10 ) 2 preferably NH 2 and N (CH 3 ) 2 ,
• C 2-2 o-alkylaminoalkyl preferably Cz-i ⁇ -alkylaminoalkyl, such as methylaminomethyl, 2-methylaminoethyl, ethylaminomethyl, 2-ethylaminoethyl and 2- (iso-propylamino) ethyl, C3- 2 o-dialkylaminoalkyl, preferably C3-1 6-dialkylaminoalkyl such as dimethylamino methyl, 2-dimethylaminoethyl, 2-diethylaminoethyl, 2- (di-n-propylamino) ethyl and 2- (di-iso-propylamino) ethyl,
• J 1 I an integer from 1 to 4 (1, 2, 3 or 4), preferably 2 and 3, particularly preferably 2,
• 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 an integer from 1 to 8 (1, 2, 3, 4, 5, 6, 7 or 8), more preferably an integer from 1 to 6.
• Suitable ketones which can be used in the process according to the invention are suitable among the above-mentioned. Prerequisites practically all aliphatic and aromatic ketones.
• the aliphatic ketones can be straight-chain, branched or cyclic, the ketones can 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, alkenyloxy, alkylamino or dialkylamino groups, or else optionally hydrogenated under the conditions of the hydrogenating amination be CC double or triple bonds. If polyvalent 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:
• aldehydes which can be used in the process according to the invention, virtually all aliphatic and aromatic aldehydes are suitable under the abovementioned conditions.
• the aliphatic aldehydes may be straight-chain, branched or cyclic, the aldehydes may contain heteroatoms.
• the aldehydes 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. If polyvalent aldehydes or keto aldehydes are aminated, it is possible to obtain control of the reaction conditions in hand, amino alcohols, cyclic amines or multiply aminated products.
• aldehydes are preferably hydrogenated aminatively:
• aminating agents in the hydrogenating amination of aldehydes and / or ketones in the presence of hydrogen it is possible to use primary or secondary, aliphatic or cycloaliphatic or aromatic amines.
• cyclic amines such as e.g. Pyrrolidines, piperidines, hexamethyleneimines, piperazines and morpholines.
• the primary or secondary amines are preferably used as aminating agents for the preparation of unsymmetrically substituted di- or trialkylamines, such as ethyldiisopropylamine and ethyldicyclohexylamine.
• the following mono- and dialkylamines are used as aminating agents: methylamine, dimethylamine, ethylamine, diethylamine, n-propylamine, di-n-propylamine, isopropylamine, di-isopropylamine, isopropylethylamine, n-butylamine, di-n-propylamine.
• Amines particularly preferably prepared by the process according to the invention are, for example, N, N-di (C 1-4 -alkyl) cyclohexylamine (from cyclohexanone and di (C 1-4 -alkyl) amine), n-propylamine (such as dimethylpropylamine) (from propionaldehyde and DMA), N 1 N-dimethyl-N-isopropylamine (from acetone and DMA), N, N-Dimethy!
• N-N-butylamine from butanal, i-butanal or butanone and DMA
• N-ethyl-N, N diisopropylamine from acetaldehyde and N, N-diisopropylamine
• tris (2-ethylhexyl) amine (from 2-ethylhexanal and di (2-ethylhexyl) amine).
• a plant which comprised a bubble column equipped with a thin-film catalyst.
• the carbonyl compound and the amine to be reacted were placed in the reactor in which the respective thin-film catalyst was installed.
• Hydrogen was injected and the mixture was heated to reaction temperature.
• Hydrogen gas and liquid were introduced into the reactor from below. The liquid and gas were circulated in a circle.
• reaction products were analyzed by gas chromatography (GC) (separation column DB1, length 60 m; inside diameter 0.32 mm; carrier gas helium; temperature program: 80 0 C, then 8 ° C / min to 280 0 C, finally 15 minutes isothermally at 28O 0 C).
• GC gas chromatography
• the experimental autoclave was initially charged with the aldehyde Lysmeral and the amine dimethylmorpholine in a molar ratio of 1: 1.
• Isopropanol was added to the reaction mixture (40% by weight, based on the total mass of amine and aldehyde).
• the catalyst used was a palladium-containing thin-layer catalyst based on Kantha's tissue with 490 mg Pd / m 2 .
• the noble metal content in the reaction was 0.07% by weight, based on Lysmeral.
• the autoclave and the thin-layer catalyst were rinsed with isopropanol.
• the fenpropimorph synthesis was carried out at a hydrogen pressure of 6 bar and a reaction temperature of 80 ° C.
• Lysmeral and dimethylmorpholine in the amine-aldehyde molar ratio 2.5: 1 were initially charged in the experimental autoclave.
• the reaction was carried out without addition of isopropanol as a solubilizer.
• the catalyst used was the thin-layer catalyst from Example 1.
• the noble metal content in the reaction was 0.07% by weight, based on Lysmeral.
• the reaction was carried out at a hydrogen pressure of 14 bar and a reaction temperature of 120 ° C. After a reaction time of 5 hours, a lysmeral conversion of 93% was achieved with a product selectivity of 98%.
• Example A3 In the same laboratory autoclave as in Examples 1 and 2, the same thin film catalyst was used for the synthesis of dimethylcyclohexylamine. Cyclohexanone and dimethylamine were reacted in a molar amine: ketone ratio of 1.2. The noble metal content in the reaction was 0.12% by weight based on the ketone.
• the reaction was carried out at a hydrogen pressure of 6 bar and a reaction temperature of 8O 0 C. After a reaction time of 5 hours, a conversion of 33% was determined with a product selectivity of over 98%.
• Example A4 The reaction effluent from Example 3 was reacted for a further 2.5 hours at a hydrogen pressure of 14 bar and a reaction temperature of 120 ° C. on the thin-film catalyst from Examples 1 to 3.
• the cyclohexanone conversion improved to 60% with a product selectivity of 98%.
• Lysmeral and dimethylmorpholine in the amine: aldehyde molar ratio 2.5: 1 were initially charged in the experimental autoclave.
• the catalyst used was a palladium-containing thin-layer catalyst based on carbon fabric with 1.2 g Pd / m 2 .
• the noble metal content in the reaction was 0.14% by weight, based on Lysmeral.
• the reaction was carried out at a hydrogen pressure of 6 bar and a reaction temperature of 80 ° C. After a reaction time of 6 hours was a Lysmeral sales of 17% with a product selectivity of 98% achieved. In the second reaction run, a lysmeral conversion of 13% at a selectivity of more than 99% was determined under the same reaction conditions after a reaction time of 6 hours.
• Lysmeral and dimethylmorpholine were initially charged in the autoclave in an amine: aldehyde mole ratio of 2.5: 1.
• the catalyst used was the thin-layer catalyst from Example 5.
• the noble metal content in the reaction was 0.14% by weight, based on Lysmeral.
• the reaction was carried out at a hydrogen pressure of 14 bar and a reaction temperature of 120 ° C. After a reaction time of 5 hours, a Lysmeral conversion of 49% was achieved with a product selectivity of over 99%.
• Cyclohexanone and dimethylamine were reacted in the molar amine: ketone ratio 1, 2.
• the catalyst used was the thin-layer catalyst from Example 5.
• the noble metal content in the reaction was 0.16 wt .-% based on the ketone.
• the reaction was carried out at a hydrogen pressure of 6 bar and a reaction temperature of 80 0 C. After a reaction time of 6 hours, a conversion of 59% was determined with a product selectivity of over 98%.
• Example A8 Cyclohexanone and dimethylamine were reacted in the molar amine: ketone ratio 1.2.
• the catalyst used was the thin-layer catalyst from Example 5.
• the noble metal content in the reaction was 0.16 wt .-% based on the ketone.
• the reaction was carried out at a hydrogen pressure of 14 bar and a reaction temperature of 12O 0 C. After a reaction time of 6 hours, a conversion of 94% was achieved with a product selectivity of over 98%.
• Lysmeral and dimethylmorpholine in the amine were initially charged in the test reactor (a total of 650 ml).
• the catalyst used was a palladium-containing thin-layer catalyst based on Kanthal 900 fabric with 1.96 g Pd / m 2 .
• the noble metal content in the reaction was 0.14% by weight, based on Lysmeral.
• the reaction was carried out at a hydrogen pressure of 6 bar and a liquid inlet temperature of 60 0 C. It was driven with 40-105 liters / h of circulating gas.
• the circular liquid flow was 500-1000 g / min. It was driven with about 50 Ni / h of exhaust gas.
• a Lysmeral conversion of 24% was achieved with a product selectivity of over 98%.
• the reaction was conducted at a hydrogen pressure of 6 bar and a liquid inlet temperature of 6O 0 C. It was driven with 40-105 liters / h of circulating gas. The circular liquid flow was 400-750 g / min. It was driven with about 50 Nl / h of exhaust gas. After a reaction time of 5 hours, a Lysmeral conversion of 5% was achieved with a product selectivity of over 98%.

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