WO2014012908A1 - Procédé, catalysé par un complexe carbène de métal de transition, pour la préparation d'esters d'acides carboxyliques par déshydrogénation à partir d'alcools - Google Patents

Procédé, catalysé par un complexe carbène de métal de transition, pour la préparation d'esters d'acides carboxyliques par déshydrogénation à partir d'alcools Download PDF

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Publication number
WO2014012908A1
WO2014012908A1 PCT/EP2013/064957 EP2013064957W WO2014012908A1 WO 2014012908 A1 WO2014012908 A1 WO 2014012908A1 EP 2013064957 W EP2013064957 W EP 2013064957W WO 2014012908 A1 WO2014012908 A1 WO 2014012908A1
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WO
WIPO (PCT)
Prior art keywords
transition metal
primary
reaction
mixture
alcohol
Prior art date
Application number
PCT/EP2013/064957
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German (de)
English (en)
Inventor
Thomas Schaub
Stefan Rüdenauer
Daniel Schneider
Rocco Paciello
Original Assignee
Basf Se
Basf Schweiz Ag
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Basf Se, Basf Schweiz Ag filed Critical Basf Se
Priority to MX2015000827A priority Critical patent/MX2015000827A/es
Priority to JP2015522067A priority patent/JP2015526414A/ja
Priority to CN201380037308.7A priority patent/CN104470887B/zh
Priority to EP13739190.0A priority patent/EP2874991A1/fr
Publication of WO2014012908A1 publication Critical patent/WO2014012908A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/76—Dehydrogenation
    • B01J2231/763—Dehydrogenation of -CH-XH (X= O, NH/N, S) to -C=X or -CX triple bond species
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/827—Iridium

Definitions

  • the present invention relates to a process for the preparation of carboxylic acid esters by reacting at least one primary monoalcohol or a mixture of a primary monoalcohol and at least one different alcohol in the presence of a transition metal carbene complex catalyst K.
  • Carboxylic acid esters are important chemical compounds which are used, for example, as solvents, plasticizers and Fragrances and flavorings are used.
  • Organometallics 201 1, 30, 6044-6048 describes ruthenium complex compounds based on N-heterocyclic carbenes as catalysts in the direct ester formation from primary alcohols.
  • the ruthenium complex is advantageously added a phosphine.
  • catalysts K which contain at least one transition metal atom selected from ruthenium and iridium. Particularly preferred transition metal is ruthenium.
  • R 1 and R 4 independently of one another are C 1 -C 10 -alkyl, C 3 -C 10 -cycloalkyl, 5 to 10-membered heteroaryl which has 1, 2 or 3 heteroatoms selected from O, N and S as ring members or aryl, the four last-mentioned substituents are unsubstituted or may be substituted by one or more substituents selected from halogen, C 1 -C 10 -alkoxy, CN, C 1 -C 10 -alkyl, C 3 -C 10 -cycloalkyl, phenyl and naphthyl;
  • C3-Cio-Cycloalkyl represents a mono-, di-, tri- or tetracyclic alkyl radical having 3 to 10 carbon atoms. Examples are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and adamantyl.
  • Aryl represents an aromatic hydrocarbon radical which may be substituted or unsubstituted.
  • unsubstituted aryl are phenyl, 1-naphthyl, 2-naphthyl and 9-anthryl.
  • aryl which may be substituted with one or more C 1 -C 10 alkyl radicals as defined above are 2,6-di (isopropyl) phenyl, o-tolyl, m-tolyl, p-tolyl and mesityl.
  • Ci-Cio-alkoxy stands for an alkyl group having 1 to 10 carbon atoms bonded via an oxygen atom.
  • Carbocyclic aromatics are unsubstituted or monosubstituted or polysubstituted with alkyl residues aromatic compounds having generally 6 to 10 carbon atoms. Examples are benzene, naphthalene and p-cymene.
  • Aldehydes are linear or branched aldehydes, generally having 1 to 10 carbon atoms. Examples are formaldehyde, acetaldehyde and propionaldehyde.
  • Ketones are linear or branched ketones, generally having from 3 to 10 carbon atoms. Examples are acetone, butanone, 2-pentanone and 3-pentanone.
  • Ci-Cio-carboxylate are anions of saturated or unsaturated carboxylic acids having 1 to 10, in particular 1 to 4 carbon atoms.
  • Examples of C 1 -C 10 -carboxylate are formate, acetate, acrylate, methacrylate and propionate.
  • C 1 -C 10 -alkoxide are radicals of linear or branched alcohols having 1 to 10, in particular 1 to 4, carbon atoms. Examples are methoxide, ethoxide, propoxide, n-butylate, 2-butylate and tert-butylate.
  • Imidazolium salts which can be used in the process according to the invention are, above all, imidazolium salts of the general formula (II)
  • R 1 , R 2 , R 3 and R 4 have the abovementioned meanings, in particular the meanings given there as being preferred, in particular or specifically indicated,
  • A stands for H or COO " and x- for the equivalent of an anion, in particular for halide, C 1 -C 10 -carboxylate, benzoate, MeCeHUCOO " , tosylate, methanesulfonate, trifluoromethanesulfonate, mesylate, cyanide, isocyanate, thiocyanate, tetrachloroaluminate, tetrabromoaluminate, tetrafluoroborate, hexafluorophosphate , Hexafluoroantimonate, sulfate, hydroxide
  • X- is preferably chloride, tosylate, methanesulfonate, trifluoromethanesulfonate, mesylate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, C 1 -C 10 -carboxylate, sulfate or methylsulfate, in particular chloride, methanesulfonate or C 1 -C 10 -carboxylate.
  • Examples of suitable imidazolium salts of the formula (II) are 1,3-dimethylimidazolium salts, 1-methyl-3-iso-propylimidazolium salts, 1,3-diethylimidazolium salts, 1-methyl-3-n-propylimidazolium salts, 1-methyl- 4-n-butylimidazoliumsalze,
  • the imidazolium salts on which the N-heterocyclic carbenes are based are commercially available and are known, for example, as ionic liquids as well as solvents.
  • B3 alkali metal hydrides in particular LiH, NaH, KH
  • B8 alkali metal phosphates especially K3PO4, Na3P0 4 B9 alkyl lithium compounds, in particular n-butyllithium, methyllithium, tert-butyllithium
  • R 6 and R 7 independently of one another are substituted or unsubstituted C 1 -C 10 -alkyl, C 1 -C 4 -alkyl-P (phenyl) 2, C 1 -C 10 -cycloalkyl, C 3 -C 10 -alkyl Heterocyclyl, in which C 3 -C 10 -heterocyclyl contains at least one heteroatom, selected from among N, O and S, Cs-Cu- aryl or Cs -do-
  • Suitable transition metal compounds V are complex compounds and salts of the transition metals of groups 8, 9 and 10 of the Periodic Table (I UPAC), preferably complex compounds and salts of ruthenium and iridium, particularly preferably complex compounds and salts of ruthenium.
  • I UPAC Periodic Table
  • the primary monoalcohols can be linear, branched or cyclic.
  • the primary monoalcohols usually have 3 to 10 carbon atoms.
  • the primary monoalcohols generally have no further functional groups besides the one hydroxyl group.
  • the primary monoalcohols are primary alkanols having preferably 3 to 10 C atoms, primary hydroxy-C 1 -C 4 -alkyl benzenes, and primary hydroxy-C 1 -C 4 -alkyl-C 3 -C 8 -cycloalkanes.
  • the alcohols other than primary monoalcohols are secondary or tertiary alkanols having preferably 3 to 10 C atoms, cycloalkanols having preferably 5 to 10 C atoms, secondary or tertiary hydroxy-C 1 -C 4 -alkylbenzenes and secondary or tertiary hydroxy -C-C4-alkyl-C3-C8-cycloalkanes.
  • examples of such alcohols are isopropanol, 2-butanol, tert-butanol, cyclopentanol, cyclohexanol, 1-phenylethanol, phenol or 1-methyl-n-butanol.
  • mixtures of different alcohols which are obtained from fermentative sources for example mixtures of 3-methyl-n-butanol and 2-methyl-n-butanol, which are obtained as by-products in the industrial production of bioethanol (so-called "fusel oils”).
  • the primary monoalcohols as well as the optionally used further alcohols may moreover bear substituents which undergo reaction under the reaction conditions. inert behavior of the process according to the invention, for example alkoxy, alkene oxy, dialkylamino and halogen (F, Cl, Br, I).
  • a primary aliphatic C3-Cio-alcohol or a mixture of primary aliphatic C3-Cio-alcohols in particular a primary aliphatic C4-C6-alcohol or a mixture of primary aliphatic C4-C6-alcohols, to ,
  • the primary monoalcohol is isoamyl alcohol or a mixture of isoamyl alcohol with 2-methyl-n-butanol.
  • the process according to the invention takes place in the presence of a transition metal carbene complex catalyst K, as defined above. It has proved to be advantageous if the catalytically active part of the catalyst K is at least partially dissolved in the liquid reaction medium. In a preferred embodiment, at least 90% of the catalyst used in the process K are dissolved in the liquid reaction medium, more preferably at least 95% and most preferably more than 99%, each based on the total amount in the liquid reaction medium.
  • the previously defined transition metal carbene complex catalyst K is prepared by reacting a transition metal compound V with an imidazolium salt in the presence of the primary monoalcohol and the base.
  • the amount of the metal component of the catalyst preferably ruthenium or iridium, is generally 0.1 to 5000 ppm (parts by weight), in particular in the range of 1 to 2000 ppm, especially 50 to 1000 ppm, each based on the total weight of the liquid reaction mixture.
  • the base is preferably used in an amount of 1 to 20 equivalents of base, in particular in an amount of 1 to 5 equivalents of base, based on 1 equivalent of the imidazolium salt.
  • the imidazolium salt is used preferably in an amount of 1 to 20 mol, especially in an amount of 1 to 6 mol, based on 1 mol of the transition metal in the transition metal compound V.
  • the reaction of the primary monoalcohol or the mixture of a primary monoalcohol and at least one different alcohol is generally carried out at a temperature in the range of 20 to 250 ° C.
  • the process according to the invention is preferably carried out at temperatures in the range from 100.degree. C. to 200.degree. C., more preferably in the range from 110.degree. To 200.degree.
  • the reaction of the primary monoalcohol or the mixture of a primary monoalcohol and at least one different alcohol is generally at a total pressure of 0.1 to 20 MPa absolute, which is both the autogenous pressure of the alcohols or of the alcohol at the reaction temperature and the pressure a gas such as nitrogen, argon or hydrogen can be carried out.
  • the process according to the invention is preferably carried out absolutely at a total pressure of up to 10 MPa absolute, in particular at a total pressure of up to 1 MPa.
  • the reaction of the primary monoalcohol or the reaction of the mixture of a primary monoalcohol and at least one different alcohol will lead to the extent that the conversion, based on the primary monoalcohol, at least 10%, in particular at least 20% and especially at least 25%. It has proven to be advantageous not to carry out the reaction up to full conversion (100%, based on the primary monoalcohol), but only up to a conversion of not more than 80%, in particular not more than 70%.
  • the time required for this reaction can the expert determine by routine tests. It is generally in the range of 15 minutes to 100 hours, especially in the range of 1 hour to 50 hours.
  • the esterification of the primary alcohol or the mixture of a primary monoalcohol and at least one different alcohol is naturally carried out with elimination of hydrogen (see above reaction equations). It has proven to be advantageous to remove the hydrogen from the reaction system. In this way you can increase sales. This is achieved either by stripping with the boiling unreacted alcohol or by supplying a stripping gas such as nitrogen, carbon dioxide or argon.
  • the reaction can be carried out in the customary devices or reactors known to those skilled in the art for liquid-gas reactions in which the catalyst is homogeneously dissolved in the liquid phase.
  • the process according to the invention it is possible in principle to use all reactors which are fundamentally suitable for gas-liquid reactions under the given temperature and the given pressure.
  • Suitable standard reactors for gas-liquid and liquid-liquid reaction systems are described, for example, in KD Henkel, "Reactor Types and Their Industrial Applications", Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH Verlag GmbH & Co. KGaA, Chapter 3.3: "Reactors for gas-liquid reactions", to which reference is hereby made. Examples which may be mentioned stirred tank reactors, tubular reactors or bubble column reactors.
  • the supply of alcohol, transition metal compound V, imidazolium salt and the base can be carried out simultaneously or separately.
  • the reaction can be carried out discontinuously in batch mode or continuously, semicontinuously with recycling or without recycling.
  • the average residence time in the reaction space is generally 15 minutes to 100 hours, in particular 1 hour to 50 hours.
  • the carboxylic ester is usually separated from unreacted alcohol, preferably by distillation.
  • the catalyst K remains with the high boilers in the bottom of the distillation and can be reused. Unreacted alcohol can be recycled back into the reaction.
  • the thermal separation of the alcohol or of the alcohols and of the carboxylic acid ester takes place by the methods known to those skilled in the art, preferably in an evaporator or in a distillation unit, comprising evaporator and column (s), which usually has several trays, a packing or packing.
  • the mixture was heated for 20 h with stirring (magnetic stirrer) at normal pressure and 170 ° C oil bath temperature under reflux. After the end of the reaction, 72.6% unreacted starting material mixture and 27.1% of the carboxylic acid ester (mixture of isomers, formed from 3-methyl-n-butanol and 2-methyl-n-butanol, conversion determined by GC-FI%) were present in the reaction mixture. From the reaction, 46.3 g were distilled off on a rotary evaporator (80 ° C oil bath temperature, 20 mbar) (mixture of educt mixture and carboxylic acid ester). The catalyst and the base remained in the liquid residue and could be reused.
  • a rotary evaporator 80 ° C oil bath temperature, 20 mbar

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de préparation d'esters d'acides carboxyliques, comprenant la réaction d'au moins un alcool monohydrique primaire ou d'un mélange d'un alcool monohydrique primaire et d'au moins un alcool différent de ce dernier en présence d'un catalyseur constitué d'un complexe carbène de métal de transition (K), lequel comporte comme atome central (M) au moins un atome de métal de transition du groupe 8, 9 ou 10 du tableau périodique des éléments (IUPAC) et au moins un ligand carbène N-hétérocyclique monodente, en présence d'une base. Selon l'invention, on prépare le catalyseur (K) par réaction d'un composé d'un métal de transition (V) qui comporte au moins un atome de métal de transition du groupe 8, 9 ou 10 du tableau périodique des éléments (IUPAC), mais pas de ligand carbène, avec un sel d'imidazolium en présence de l'alcool monohydrique primaire et de la base, lors de quoi on procède à la transformation en la substance.
PCT/EP2013/064957 2012-07-17 2013-07-16 Procédé, catalysé par un complexe carbène de métal de transition, pour la préparation d'esters d'acides carboxyliques par déshydrogénation à partir d'alcools WO2014012908A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
MX2015000827A MX2015000827A (es) 2012-07-17 2013-07-16 Metodo catalizado por el complejo carbeno de metal de trasicion para producir esteres del acido carboxilico a partir de alcoholes bajo deshidratacion.
JP2015522067A JP2015526414A (ja) 2012-07-17 2013-07-16 脱水下でアルコールからカルボン酸エステルを製造する遷移金属カルベン錯体触媒法
CN201380037308.7A CN104470887B (zh) 2012-07-17 2013-07-16 在脱水下由醇制备羧酸酯的过渡金属卡宾配合物催化方法
EP13739190.0A EP2874991A1 (fr) 2012-07-17 2013-07-16 Procédé, catalysé par un complexe carbène de métal de transition, pour la préparation d'esters d'acides carboxyliques par déshydrogénation à partir d'alcools

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP12176700 2012-07-17
EP12176700.8 2012-07-17

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WO2014012908A1 true WO2014012908A1 (fr) 2014-01-23

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EP (1) EP2874991A1 (fr)
JP (1) JP2015526414A (fr)
CN (1) CN104470887B (fr)
MX (1) MX2015000827A (fr)
WO (1) WO2014012908A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015173276A1 (fr) * 2014-05-16 2015-11-19 Basf Se Procédé de préparation d'un sel d'acide carboxylique insaturé
WO2015173295A1 (fr) * 2014-05-16 2015-11-19 Basf Se Préparation d'un sel d'acide carboxylique insaturé à partir d'un alcène et de dioxyde de carbone à l'aide d'un complexe de métal de transition immobilisé de manière covalente

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010058004A1 (fr) * 2008-11-24 2010-05-27 Technical University Of Denmark Procédé pour la préparation d'amides à partir d'alcools et d'amines par élimination d'hydrogène
WO2012052996A2 (fr) * 2010-10-19 2012-04-26 Yeda Research And Development Co. Ltd. Nouveaux complexes de ruthénium et leurs utilisations dans des procédés de préparation et/ou d'hydrogénation d'esters, d'amides et de leurs dérivés

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010058004A1 (fr) * 2008-11-24 2010-05-27 Technical University Of Denmark Procédé pour la préparation d'amides à partir d'alcools et d'amines par élimination d'hydrogène
WO2012052996A2 (fr) * 2010-10-19 2012-04-26 Yeda Research And Development Co. Ltd. Nouveaux complexes de ruthénium et leurs utilisations dans des procédés de préparation et/ou d'hydrogénation d'esters, d'amides et de leurs dérivés

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See also references of EP2874991A1 *
SOLVHOI ET AL.: "Dehydrogenative Coupling of Primary Alcohols To Form Esters Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex", ORGANOMETALLICS, vol. 30, 14 October 2011 (2011-10-14), pages 6044 - 6048, XP002712036 *
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015173276A1 (fr) * 2014-05-16 2015-11-19 Basf Se Procédé de préparation d'un sel d'acide carboxylique insaturé
WO2015173295A1 (fr) * 2014-05-16 2015-11-19 Basf Se Préparation d'un sel d'acide carboxylique insaturé à partir d'un alcène et de dioxyde de carbone à l'aide d'un complexe de métal de transition immobilisé de manière covalente
CN106458823A (zh) * 2014-05-16 2017-02-22 巴斯夫欧洲公司 制备不饱和羧酸盐的方法
US10011551B2 (en) 2014-05-16 2018-07-03 Basf Se Process for preparing an unsaturated carboxylic acid salt
CN106458823B (zh) * 2014-05-16 2022-04-19 巴斯夫欧洲公司 制备不饱和羧酸盐的方法

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Publication number Publication date
CN104470887B (zh) 2016-11-09
JP2015526414A (ja) 2015-09-10
MX2015000827A (es) 2015-09-28
EP2874991A1 (fr) 2015-05-27
CN104470887A (zh) 2015-03-25

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