EP0901455A1 - Procede d'hydrogenation catalytique de terpenoides - Google Patents

Procede d'hydrogenation catalytique de terpenoides

Info

Publication number
EP0901455A1
EP0901455A1 EP97923923A EP97923923A EP0901455A1 EP 0901455 A1 EP0901455 A1 EP 0901455A1 EP 97923923 A EP97923923 A EP 97923923A EP 97923923 A EP97923923 A EP 97923923A EP 0901455 A1 EP0901455 A1 EP 0901455A1
Authority
EP
European Patent Office
Prior art keywords
hydrogenation
catalyst
transition metal
group
hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97923923A
Other languages
German (de)
English (en)
Inventor
Ernst Bayer
Wilhelm Schumann
Sebastian Erber
Klaus-Peter Stengele
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nigu Chemie GmbH
Original Assignee
Nigu Chemie GmbH
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 Nigu Chemie GmbH filed Critical Nigu Chemie GmbH
Publication of EP0901455A1 publication Critical patent/EP0901455A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
    • C12C5/00—Other raw materials for the preparation of beer
    • C12C5/02—Additives for beer
    • C12C5/026—Beer flavouring preparations
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B35/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving a change in the type of bonding between two carbon atoms already directly linked
    • C07B35/02—Reduction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
    • C12C3/00—Treatment of hops
    • C12C3/12—Isomerised products from hops
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
    • C12C9/00—Methods specially adapted for the making of beerwort
    • C12C9/02—Beerwort treatment; Boiling with hops; Hop extraction
    • C12C9/025—Preparation of hop extracts; Isomerisation of these extracts; Treatment of beerwort with these extracts; Surrogates of the hop
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers

Definitions

  • the present invention relates to a process for the catalytic hydrogenation of terpenoids in the presence of a transition metal catalyst in a homogeneous phase.
  • terpenoid compounds Due to their natural occurrence and the associated physiological harmlessness, terpenoid compounds play an increasingly important role, for example in the food, luxury food or cosmetics industries.
  • hop ingredients such as humulones, isohumulones or lupulones, which are known to be used as condiments in brewing beer.
  • a disadvantage here is the low lightfastness of these hop ingredients, so that special precautions are required when storing the beer so that there is no undesirable change in the smell or taste.
  • terpenoids Another example of the chemical modification of terpenoids is the hydrogenation of squalene (2,6,10,15, 19,23-hexamethyl-2,6,10,14,18,22-tetrakosahexaene) to squalane, which on a large scale is used as an ointment base in pharmaceutical or cosmetic preparations.
  • the hydrogenation processes known for the production of squalane also have the serious disadvantage that they are technically very complex and cause comparatively high operating and investment costs.
  • the present invention was therefore based on the object of developing a process for the catalytic hydrogenation of terpenoids with hydrogen in the presence of a transition metal catalyst which does not have the disadvantages of the prior art mentioned, but also extensive hydrogenation of the corresponding starting compounds with little technical outlay enables.
  • transition metals of the eighth subgroup of the periodic table consist of a reaction product of transition metals of the eighth subgroup of the periodic table and special polymer compounds.
  • the metals are Palladium, platinum, nickel, rhodium and ruthenium and mixtures of these metals are to be regarded as particularly preferred. Mixtures of palladium and platinum, for example, have proven particularly useful.
  • the polymer component of the catalyst used according to the invention consists of polyvinylpyrrolidone (PVP), polyethyleneimine (PEI) derivatives or starch derivatives.
  • PVP polyvinylpyrrolidone
  • PEI polyethyleneimine
  • starch derivatives polyvinylpyrrolidones with a relatively low molecular weight of approximately 10,000 to 50,000 are preferably used here.
  • Polyethyleneimine derivatives include both polyethyleneimines with a preferred molecular weight of 1,000 to 50,000 or derivatized compounds
  • the derivatization can be carried out with the appropriate alkylating agents (such as methyl iodide or dimethyl sulfate), acylating agents (such as acetic anhydride) or epoxidation reagents (such as ethylene oxide, propylene oxide etc.).
  • alkylating agents such as methyl iodide or dimethyl sulfate
  • acylating agents such as acetic anhydride
  • epoxidation reagents such as ethylene oxide, propylene oxide etc.
  • the degree of derivatization of the polyethyleneimines is relatively unproblematic, i. H.
  • the primary and secondary amino groups of the polyethyleneimine can, if desired, be derivatized in whole or in part.
  • starch derivatives for the polymer compounds used according to the invention.
  • a carboxymethylated starch with a degree of substitution of 0.5 to 3.0 is used as the starch derivative.
  • the ratio of transition metal to polymer compound can be varied within wide limits within the scope of the present invention, but it has proven to be particularly advantageous to set the quantitative ratio of transition metal to polymer compound to 1:20 to 1:50.
  • the catalytic hydrogenation reaction takes place in a homogeneous phase, because only in this way can rapid hydrogenation also take place under mild conditions.
  • the hydrogenation reaction will preferably carried out in water or in alkaline aqueous solution, provided that the corresponding Te ⁇ enoide dissolve in these media.
  • alkaline solution it is preferred to work in alkaline solution at a pH of 7.0 to 10.0.
  • alcohols with 1 to 4 carbon atoms can also be used as solvents, where in the case of
  • reaction temperature in the process according to the invention can also be varied within certain limits and depends essentially on the
  • the reaction pressure is also relatively uncritical, i.e. it can be carried out either at normal pressure or to accelerate the reaction rate at an overpressure which, depending on the autoclaves available, can be up to 50 bar.
  • the preparation of the catalysts used according to the invention is technically relatively easy to carry out and is described, for example, in US Pat. No. 4,419,490.
  • a salt of the transition metal used is placed in a suitable solvent, then the polymer compound is optionally also added in dissolved form and finally the catalyst with a reducing agent such as e.g. Sodium borohydride (NaBH4) or hydrogen, reduced.
  • a reducing agent such as e.g. Sodium borohydride (NaBH4) or hydrogen, reduced.
  • the corresponding terpenoid can be added to the catalyst solution without prior isolation of the catalyst and the hydrogenation can be carried out under the respective reaction conditions, the hydrogen being preferably used in excess.
  • Te ⁇ enoide within the scope of the present invention, hop ingredients such as.
  • humulon, isohumulon or lupulon, or squalene can be used.
  • the catalyst is separated off by customary methods, for example by ultrafiltration, and can easily be used again for hydrogenation reactions.
  • the separated filtrate with the dissolved product can, if necessary, be isolated by removing the solvent or can be analyzed, for example, by HPLC or GC.
  • the teipenoids used according to the invention are practically quantitatively hydrogenated, and neither the corresponding starting compounds nor any partially hydrogenated intermediates can be found.
  • 0.3 ml of a methanolic Li2PdCl4 solution (palladium content: 3 mg) is diluted with 20 ml of ethanol, mixed with 5 ml of a 2% by weight aqueous PVP solution (K value: 25) and then with 5 mg sodium borohydride reduced at room temperature (duration: 15 minutes). Then 400 mg of isohumulone dissolved in 10 ml of ethanol are added to the catalyst solution and hydrogenated at room temperature and 1 bar within 3 hours (hydrogen absorption: 45 ml). The catalyst is then largely separated by ultrafiltration and the filtrate is analyzed by HPLC. The evaluation of the corresponding chromatogram shows that an almost quantitative hydrogenation of the exocyclic double bonds has occurred since neither the starting compound nor the dihydro compound was found.
  • 0.3 ml of a methanolic L ⁇ 2PdCl4 solution (palladium content: 3 mg) is diluted with 20 ml of ethanol, with 5 ml of a 2% by weight aqueous solution of acetylated PEI (degree of acetylation approx. 25%; MW approx. 50 000) and then reduced with excess hydrogen at room temperature (duration: 30 minutes). 400 mg of isohumulone in 10 ml of ethanol are then added to the catalyst solution and the mixture is hydrogenated at room temperature and 1 bar for 3.5 hours (hydrogen absorption: 45 ml). The subsequent analysis by HPLC shows an almost quantitative hydrogenation of the exocyclic double bonds.
  • aqueous Na2PdC.4 solution palladium content: 3 mg
  • aqueous PVP solution K value: 25
  • excess hydrogen at room temperature (duration: 30 minutes).
  • 4 ml of a 10.5% strength aqueous isohumulone solution are added to the catalyst solution and hydrogenated at room temperature and 1 bar for about 10 hours (hydrogen absorption: 45 ml).
  • the subsequent analysis by HPLC shows an almost quantitative hydrogenation of the exocyclic double bonds.
  • aqueous Na2PdCl4 solution (palladium content: 10 mg) is diluted in 30 ml of water with 20 ml of a 2% by weight aqueous solution of acetylated PEI (degree of acetylation approx. 25%; MW approx. 50,000 ) and then reduced with excess hydrogen at room temperature (duration: 30 minutes). After the reduction has taken place, 40 ml of a 10% strength by weight aqueous isohumulone solution are added to the catalyst solution and hydrogenated at a temperature of 50 ° C. and normal pressure for about 8 hours (hydrogen absorption: 450 ml).
  • the catalyst is separated from the hydrogenated isohumulone by means of ultrafiltration using a UV membrane with an exclusion limit of approximately 10,000 daltons. After redissolving, the catalyst can be used again for the hydrogenation. Analysis by HPLC shows a practically quantitative hydrogenation of the exocyclic double bonds.
  • a methanolic Li2PdCl4 solution (palladium content: 3 mg) is diluted with 20 ml of ethanol, mixed with 5 ml of a 2% by weight ethanolic PVP solution (K value: 25) and the solution with Reduced hydrogen.
  • K value 2% by weight ethanolic PVP solution
  • 300 mg of humulon, dissolved in 10 ml of ethanol are added and the mixture is hydrogenated at room temperature and 1 bar of hydrogen pressure for 1 hour (hydrogen uptake: 30 ml).
  • the soluble polymeric hydrogenation catalyst is separated by means of ultrafiltration (membrane with exclusion limit of 10,000 daltons), and the filtrate is analyzed by means of HPLC. The spectrum shows that the humulon used was almost completely hydrogenated to tetrahydrohumulon.
  • 0.3 ml of a methanolic Li2PdCl4 solution (palladium content: 3 mg) is diluted with 20 ml of n-butanol, mixed with 2 ml of a 2% by weight aqueous solution of alkylated PEI (degree of alkylation approx. 50%) and then reduced with 5 mg sodium borohydride at room temperature (duration: 15 minutes). Then 2 g of squalene are added and the hydrogenation is carried out at 50 ° C. and 1 bar for a period of 3 hours (hydrogen uptake: 600 ml). The catalyst is then separated off by ultrafiltration and the filtrate is spun in. The yield is 1.92 g of squalane (yield: 93.7%) with a gas chromatographic purity of over 99%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Zoology (AREA)
  • General Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Genetics & Genomics (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé d'hydrogénation catalytique de terpénoïdes avec de l'hydrogène en présence d'un catalyseur à base de métaux de transition, procédé selon lequel on réalise l'hydrogénation en phase homogène en présence d'un catalyseur constitué d'un produit de réaction de métaux de transition du huitième sous-groupe et de composés polymères sélectionnés dans le groupe des polyvinylpyrrolidones (PVP), des dérivés de polyéthylène-imine (PEI) ou des dérivés d'amidon. Ce procédé permet d'hydrogéner les terpénoïdes de façon pratiquement quantitative dans des conditions non agressives.
EP97923923A 1996-05-20 1997-05-16 Procede d'hydrogenation catalytique de terpenoides Withdrawn EP0901455A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19620171 1996-05-20
DE1996120171 DE19620171A1 (de) 1996-05-20 1996-05-20 Verfahren zur katalytischen Hydrierung von Terpenoiden
PCT/EP1997/002525 WO1997044304A1 (fr) 1996-05-20 1997-05-16 Procede d'hydrogenation catalytique de terpenoides

Publications (1)

Publication Number Publication Date
EP0901455A1 true EP0901455A1 (fr) 1999-03-17

Family

ID=7794742

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97923923A Withdrawn EP0901455A1 (fr) 1996-05-20 1997-05-16 Procede d'hydrogenation catalytique de terpenoides

Country Status (4)

Country Link
EP (1) EP0901455A1 (fr)
AU (1) AU2956797A (fr)
DE (1) DE19620171A1 (fr)
WO (1) WO1997044304A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6303824B1 (en) * 1999-11-11 2001-10-16 Miller Brewing Company Method of hydrogenating iso-α acids in a buffered solution
EP1236512A1 (fr) * 2001-02-28 2002-09-04 Council Of Scientific And Industrial Research Catalyseur de métal précieux à taille nano et procédé de préparation sélective de 1,4 butènediol
US20110117252A1 (en) * 2009-11-13 2011-05-19 Kalamazoo Holdings, Inc. Process for the preparation of tetrahydroisohumulone compositions
GB201009873D0 (en) 2010-06-14 2010-07-21 Univ Leuven Kath Method for hydrogenation of isoalpha-acids (isohumulones) to hexahydro-iso-alpha-acids (hexahydro-isohumulones) by using heterogeneous ruthenium
CN106519086B (zh) * 2016-11-03 2018-10-02 哈尔滨工业大学 一种聚乙烯吡咯烷亚氨高分子化合物及其制备方法和应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2966350D1 (en) * 1978-08-17 1983-12-01 Heyl Chem Pharm Polymeric hydrogenation catalysts, process for preparing these catalysts and their use for catalytic hydrogenations
ES2004269A6 (es) * 1987-03-25 1988-12-16 Tadeval S A Procedimiento para la obtencion de escualano
US5013571A (en) * 1990-01-31 1991-05-07 Pfizer Inc. Methods for making tetrahydroisoalpha and hexahydroisoalpha acids
US5296637A (en) * 1992-12-31 1994-03-22 Kalamazoo Holdings, Inc. Production of odor-free tetrahydroisohumulates from alpha acids via their tetrahydrohumulates and subsequent isomerization
US5600012A (en) * 1995-04-06 1997-02-04 John I. Haas, Inc. Process for producing tetrahydroisoalpha acids

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9744304A1 *

Also Published As

Publication number Publication date
DE19620171A1 (de) 1997-11-27
WO1997044304A1 (fr) 1997-11-27
AU2956797A (en) 1997-12-09

Similar Documents

Publication Publication Date Title
DE69119442T2 (de) Verfahren zur Herstellung von Tetrahydroisoalpha- und Hexahydroisoalphasäuren
DE69322478T2 (de) Verfahren zur Herstellung von hypokalorischem, löslichen Polymerisat von Glukose
DE69215359T2 (de) Reduzierte polydextrose
EP2393817B1 (fr) Procédé pour préparer de la 2,6-dioxabicyclo-(3.3.0)-octan-4,8-dione
EP2332900B1 (fr) Procédé d'oxydation sélective de glucides à l'aide de catalyseurs or supportés
EP0071787B1 (fr) Catalyseurs d'hydrogénation à base de ruthénium-carbone, leur préparation et leur utilisation dans l'hydrogénation de composés carbonylés insaturés
DE3881024T2 (de) Verfahren zur herstellung von tetracyclin.
EP1165580A1 (fr) Procede catalytique permettant la modification d'hydrates de carbone, d'alcools, d'aldehydes ou de composes polyhydroxy
DE69805295T2 (de) Verfahren zur herstellung von stanolestern
EP0901455A1 (fr) Procede d'hydrogenation catalytique de terpenoides
EP0323573B1 (fr) Procédé pour la préparation de N,N-diméthylamines tertiaires
DE2816460C3 (de) Verfahren zur Herstellung von asymmetrischen N-Phenyl-N`-substituierten p-Phenylendiaminen
EP1108469B1 (fr) Activation d'un catalyseur d'hydrogénation
DE3006867C2 (de) Verfahren zur Herstellung von höheren gesättigten Ketonen
EP0347796A2 (fr) Procédé de préparation du 4-chloro-2,5-diméthoxy-aniline
DE2923949A1 (de) Katalysator fuer die katalytische hydrierung von 1,4-butindiol zu 1,4-butandiol
CH637936A5 (de) Verfahren zur herstellung von moranolin und n-methylmoranolin.
EP0024651A1 (fr) Procédé de synthèse de composés carbonyles et d'alcools oléfiniquement insaturés
DE3325983C2 (fr)
DE69706542T2 (de) Verfahren zur herstellung von xylitol
DE1228254B (de) Verfahren zur Herstellung antibakteriell wirksamer Dihydrofusidinsaeure bzw. -salze
DE60100044T2 (de) Verfahren zur Herstellung von Isoindolin
DE60206487T3 (de) Verfahren zur entsalzung einer zuckerlösung und anionenaustauscher
DE60303939T2 (de) Herstellung lichtstabiler hopfenprodukte
EP1648916B1 (fr) Procede d'obtention d'un melange naturel d'oestrogenes equins conjugues

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19981113

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IE IT LI NL PT

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 19990309