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WO2017001435A1 - Procédé de synthèse de polyènes à partir d'aldéhydes - Google Patents

Procédé de synthèse de polyènes à partir d'aldéhydes Download PDF

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Publication number
WO2017001435A1
WO2017001435A1 PCT/EP2016/065064 EP2016065064W WO2017001435A1 WO 2017001435 A1 WO2017001435 A1 WO 2017001435A1 EP 2016065064 W EP2016065064 W EP 2016065064W WO 2017001435 A1 WO2017001435 A1 WO 2017001435A1
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WIPO (PCT)
Prior art keywords
aldehydes
polyenes
polyene
catalyst
synthesis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2016/065064
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German (de)
English (en)
Inventor
Veronika KOLB
Bastian J.M. ETZOLD
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Friedrich Alexander Universitaet Erlangen Nuernberg
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Friedrich Alexander Universitaet Erlangen Nuernberg
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Publication of WO2017001435A1 publication Critical patent/WO2017001435A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
    • C07C1/2072—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by condensation
    • C07C1/2074—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by condensation of only one compound
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/28—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/20—Carbon compounds
    • C07C2527/22—Carbides

Definitions

  • the invention relates to a process for the synthesis of polyenes by reacting aldehydes.
  • Polyenes are generally understood as meaning unsaturated aliphatic hydrocarbons having a plurality of conjugated double bonds, ie alternating single and double bonds in the molecule.
  • Known polyenes are, for example, ⁇ -carotene and 1,6-diphenyl-1,3,5-hexatriene (DPH).
  • DPH 1,6-diphenyl-1,3,5-hexatriene
  • ß-carotene a symmetrical carotenoid, known as provitamin A, represents a polyene that is important for the human organism. It acts as a therapeutic agent and is converted in the body into the active substances retinol (vitamin A), retinal and retinoic acid, which are used for sugar transport , vision, as well as cell development and differentiation are important.
  • 1, 6-diphenyl-1, 3,5-hexatriene is a fluorescent tracer molecule.
  • DPH 1, 6-diphenyl-1, 3,5-hexatriene
  • E, E, E-DPH Due to its delocalized ⁇ -electron system, ⁇ , ⁇ , ⁇ - DPH has fluorescent properties. Due to its lipophilic character and its steric configuration, it specifically stores itself in organic phases such as cell membranes. Furthermore, E, E, E-DPH is also used as a dye and / or as a fluorescent marker to improve the optical properties of polymers. In the field of optics, the use of E, E, E -DPH, for example, in UV filters or LEDs is examined. Accordingly, there is currently one Numerous well-known manufacturers dealing with the synthesis of polyenes in general, and in particular with the synthesis of E, E, E -DPH.
  • the invention is as a first object to provide a method by which polyenes with respect to previous methods lesser
  • the invention is confronted in a first step with the problem that the synthesis of polyenes is usually homogeneous.
  • the set catalysts can be recovered only with great effort and corresponding costs. This directly affects the selling price of the synthesized polyene and is directly reflected in the market price.
  • homogeneous catalysts are not stereoselective with respect to the products formed, so that subsequent isomerization reactions and subsequent separation and treatment steps become necessary in the targeted production of an isomer.
  • the invention seeks alternatives to the hitherto common synthetic routes.
  • the invention provides considerations to deviate from the hitherto customary homogeneous or homogeneously catalyzed synthesis route.
  • the invention uses knowledge of heterogeneous catalysis.
  • solid catalysts are used which, in contrast to the catalysts used in homogeneous catalysis, can be easily and efficiently separated from the resulting product.
  • the activity and stereoselectivity of a corresponding catalytically active solid can be influenced by the chemical and physical parameters of its production steps.
  • metal-based solids are used as catalytically active materials essentially in the chemical industry on an industrial scale application. These include, in addition to the catalytic hydrogenation classical syntheses such as sulfuric acid or ammonia synthesis. Furthermore, metal-based catalysts are used in the mineral oil industry and in catalytic converters. Polyenes are usually synthesized as part of a fine chemical synthesis. The use of solid-state catalysts in polyene synthesis has so far resulted in low stereoselectivities and has not been considered.
  • the invention nevertheless uses a metal-based solid in the synthesis of polyenes from aldehydes and surprisingly has been able to show, on the basis of extensive investigations, that it is possible by using a metal-based solid as a catalyst, To synthesize polyenes from aldehydes.
  • metal-based solids are suitable for polyene synthesis from aldehydes.
  • the synthesis of the polyenes is stereoselective. It could be shown that the use of metal-based solids specifically leads to a polyene in the desired configuration.
  • the use of a metal-based solid catalyst recovery is enormously simplified.
  • the catalyst removal is advantageously carried out mechanically with minimal effort.
  • the catalyst can be used several times.
  • Recykli mecanicslab of at least 3 so at least three times reuse of the catalyst used, has already been successfully implemented.
  • the catalyst was regenerated between the individual cycles under hydrogen at 200 ° C.
  • the present process is a synthesis that is performed in a single step.
  • the process is environment- and material-friendly and does not require the use of sulfur, halogens or dissolved metals and metal complexes. Accordingly, the disposal costs and the Auftherapiesetzwand are much lower.
  • metal-based solids are all those which have a sufficiently large surface area for the reaction of the aldehydes and a high selectivity for the target product, ie the synthesized polyene.
  • transition metals are used as catalyst materials, in particular transition metals of the IV to VI subgroup of the periodic table are preferred.
  • a metal-based solid is used, which has a high stereoselectivity to the target product.
  • the catalyst is selected from a group which contains transition metal carbides (M x C y ), transition metal oxocarboxylides ([M x (C) (O) y]) and transition metal oxides (M x O y ).
  • M generally denotes a metal, and in particular a transition metal. More preferably, the catalyst is selected from a group containing molybdenum carbide (Mo 2 C), molybdenum oxocarbide ([Mo 2 (C) (0)]) and molybdenum oxide (MoO 3 ).
  • Mo 2 C molybdenum carbide
  • MoO 3 molybdenum oxide
  • oxidation states of the metal are between 0 (for the pure carbide) and the maximum oxidation state of the respective metal (for example + VI for molybdenum).
  • the oxo carbide has proved to be particularly favorable, in which molybdenum is present in the oxidation state +1.
  • the catalysts used have a high surface area, which favors the selective synthesis of polyenes from aldehydes. In particular, these catalysts show a stereoselectivity of 99% to the target product.
  • the catalytically active surface of the catalyst is preferably in a range between 5 m 2 / g and 200 m 2 / g.
  • the catalyst used is molybdenum carbide (Mo 2 C) having a catalytically active surface in a range between 90 m 2 / g and 1100 m 2 / g.
  • Another advantage is the use of oxocarbides as catalyst material, the catalytically active surface is in a range between 50 m 2 / g and 150 m 2 / g.
  • Preferred metal oxides have a catalytically active surface in a range between 80 m 2 / g and 90 m 2 / g.
  • the polyenes are selectively synthesized as all-trans isomers.
  • catalysts selected from a group include transition metal carbides (M x C y ), transition metal oxocarbides ([M x (C) (O) y ]), and transition metal oxides (M x O y ).
  • M x C y transition metal carbides
  • M oxocarbides [M x (C) (O) y ]
  • transition metal oxides M x O y
  • unsaturated aldehydes are used for the synthesis of polyenes having a plurality of conjugated double bonds.
  • the aldehydes are preferably selected from a group comprising 3-phenyl-2-propenal, 5-phenyl-2, 4-pentadienal, 7-phenyl-2,4,6-heptatrienal, 2,4-pentadienal, 2,4 , 6-heptatrienal and 2, 4-hexadienal.
  • DPH 3,5-hexatriene
  • the selective synthesis of E, E, E-DPH avoids in particular necessary isomerization reactions and subsequent separation and preparation.
  • the polyene is conveniently separated by crystallization. The crystallization is preferably carried out at room temperature.
  • the target product so the polyene is separated by extraction.
  • the polyene is converted into the organic phase, in which it dissolves completely.
  • the polyene is separated from the catalyst.
  • the extraction is conveniently carried out at room temperature.
  • all educts, intermediates, end products and by-products are nontoxic in the stereoselective synthesis of E, E, E-DPH.
  • E, E, E -1, 6-diphenyl-1,3,5-hexatriene is synthesized by the dimerization of 3-phenyl-2-propenal (cinnamic aldehyde) as a starting material in the presence of a metal-based solid.
  • the educt 3-phenyl-2-propenal is preferably provided as pure substance and contacted in the fluid phase with the catalyst.
  • cinnamon bark oil is used as the biogenic educt.
  • Cinnamon bark oil which is commercially available as flavor oil, is obtained from the fresh bark of the young shoots of the cinnamon tree and has a share of cinnamaldehyde of 78%.
  • the use of cinnamon bark oil thus makes it possible to recover E, E, E-DPH from renewable raw materials.
  • an open-chain polyene is synthesized by the reaction of the aldehydes.
  • a mirror-symmetric polyene is synthesized in the reaction of the aldehydes.
  • a mirror-symmetric polyene is formed when two similar aldehydes react with each other to form a polyene.
  • the open-chain, symmetrical polyenes are synthesized in a liquid-phase reaction from two molecules of the starting material, an aldehyde.
  • the aldehyde already has half the carbon skeleton of the target product, ie the polyene to be synthesized.
  • the synthesis of the polyenes takes place in a fluid phase, which preferably contains a protic solvent.
  • a fluid phase which preferably contains a protic solvent.
  • an ethanol / water mixture is used as the fluid phase.
  • the ratio of ethanol to water is preferably 3: 1.
  • the fluid phase acid is added.
  • the reaction of the aldehydes is preferably carried out in a pressure range between 1 bar and 30 bar, in particular between 10 bar and 1 5 bar, and a preferred temperature range between 75 ° C and 250 ° C, in particular between 120 ° C and 1 50 ° C.
  • E, E, E-DPH that is the trans, trans, trans isomer of 1,6-diphenyl-1,3,5-hexatriene
  • 1 shows a 1 HNMR spectrum of the synthesized (trans, trans, trans) -1, 6-diphenyl-1, 3,5-hexatriene in comparison to a literature spectrum from the database Spectral Database for Organic Compounds SDBS
  • E, E, E -DPH a 0.3 molar solution is prepared with 120 ml of ethanol, 40 ml of water and 6 g of trans-cinnamaldehyde.
  • the reaction mixture is together with 1 g molybdenum carbide catalyst (Mo 2 C) 0 x heated in a batch autoclave under nitrogen atmosphere to 135 ° C and then set a nitrogen partial pressure of 30 bar. Special attention is paid to oxygen exclusion.
  • the Mo 2 C catalyst was prepared from MoO 3 by the TPR method according to JS Lee et al., Journal of Catalysis; Vol. 106; pp 125-133, 1987:
  • the non-porous starting material Mo0 3 was heated in a temperature range of 380 ° C to 610 ° C at a rate of 40 ° C per hour and by reaction with a mixture of hydrogen and methane in a ratio of 4: 1 converted to hexagonal molybdenum carbide (Mo 2 C).
  • the reaction solution is stirred at 600 revolutions / minute (revolutions per minute, rpm) in the presence of the catalyst.
  • the reaction time is 96 hours.
  • the reaction solution is cooled. By filtration at a temperature between 65 ° C and 75 ° C, the catalyst particles are separated from the reaction solution.
  • the E, E, E-DPH precipitates in crystalline form and is separated by filtration, in this case with a filter with a mesh size of 2 ⁇ , from the other products and the solvent.
  • the solubility of the E, E, E-DPH in the ethanol / water mixture is very low at room temperature, so that 95% of the synthesized E, E, E -DPH are in the filter residue.
  • the filter residue is analyzed by means of 1 H-NMR spectroscopy, UV-Vis spectroscopy, Raman spectroscopy and TOF-MS (Time of Fligth mass spectroscopy).
  • the liquid phase, ie the filtrate, is analyzed by gas chromatography.
  • FIG. 1 shows the 1 H-NMR spectrum of the filter residue (upper spectrum in FIG. 1) in comparison to the literature spectrum (lower spectrum in FIG. 1).
  • the synthesized polyene is an isomerically pure E, E, E-1, 6-diphenyl-1, 3,5-hexatriene.

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

Abstract

L'invention concerne un procédé de synthèse de polyènes par conversion d'aldéhydes, des atomes de carbone carbonylique d'au moins deux aldéhydes dans une phase fluide formant un polyène en présence d'un catalyseur par création d'une double liaison C=C, le catalyseur utilisé étant une substance solide à base de métal.
PCT/EP2016/065064 2015-07-01 2016-06-28 Procédé de synthèse de polyènes à partir d'aldéhydes Ceased WO2017001435A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102015212361.8A DE102015212361A1 (de) 2015-07-01 2015-07-01 Verfahren zur stereoselektiven Synthese von Polyenen aus Aldehyden
DE102015212361.8 2015-07-01

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WO2017001435A1 true WO2017001435A1 (fr) 2017-01-05

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WO (1) WO2017001435A1 (fr)

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
HORACIO R. DIÉGUEZ ET AL: "Weakening C-O Bonds: Ti(III), a New Reagent for Alcohol Deoxygenation and Carbonyl Coupling Olefination", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 132, no. 1, 13 January 2010 (2010-01-13), US, pages 254 - 259, XP055301686, ISSN: 0002-7863, DOI: 10.1021/ja906083c *
J. S. LEE ET AL., JOURNAL OF CATALYSIS, vol. 106, 1987, pages 125 - 133
M.M.V RAMANA ET AL: "Microwave-assisted coupling of carbonyl compound: an efficient synthesis of olefin", JOURNAL OF CHEMICAL RESEARCH, 1 November 2004 (2004-11-01), St Albans, pages 760 - 761, XP055301689, Retrieved from the Internet <URL:http://docserver.ingentaconnect.com/deliver/connect/stl/03082342/v2004n11/s16.pdf?expires=1473680233&id=88593524&titleid=893&accname=European+Patent+Office&checksum=8DF357297CD4476A0371891C9711C9C1> DOI: 10.3184/0308234043431564 *
RACHID BAATI ET AL: "Reductive Olefination of Aldehydes via Chromium Brook Rearrangement", ORGANIC LETTERS, vol. 8, no. 14, 1 July 2006 (2006-07-01), US, pages 2949 - 2951, XP055301683, ISSN: 1523-7060, DOI: 10.1021/ol0607140 *
T. MESGANAW ET AL.: "Synthesis of Diphenylhexatriene by the Pd-Catalyzed Dimerization of Cinnamyl Acetate", J. OF ORGANIC CHEMISTRY, vol. 78, 2013, pages 3391 - 3393, XP055301673, DOI: doi:10.1021/jo400032j

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