WO2004055028A1 - Melanges contenant des complexes vanadyle-salen optiquement actifs - Google Patents

Melanges contenant des complexes vanadyle-salen optiquement actifs Download PDF

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Publication number
WO2004055028A1
WO2004055028A1 PCT/EP2003/013635 EP0313635W WO2004055028A1 WO 2004055028 A1 WO2004055028 A1 WO 2004055028A1 EP 0313635 W EP0313635 W EP 0313635W WO 2004055028 A1 WO2004055028 A1 WO 2004055028A1
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WO
WIPO (PCT)
Prior art keywords
vanadyl
salen
formula
iii
compound
Prior art date
Application number
PCT/EP2003/013635
Other languages
German (de)
English (en)
Inventor
Rainer Fell
Marion Korb
Daniel Decker
Bettina Kirschbaum
Matthias Degend
Georg Bieder
Monika Kratzer
Original Assignee
Clariant 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.)
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Publication date
Application filed by Clariant Gmbh filed Critical Clariant Gmbh
Publication of WO2004055028A1 publication Critical patent/WO2004055028A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • 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
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/005—Compounds of elements of Group 5 of the Periodic Table without metal-carbon linkages
    • 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
    • B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
    • B01J2531/56—Vanadium

Definitions

  • the invention relates to mixtures (mixtures of substances) containing optically active vanadyl salen complexes, their preparation and use.
  • Vanadyl-salen complexes can be found, as from various publications (YN Belokon et al: Tetrahedron 57 (2001), 771-779; YN Belokon et al: Org. Lett. 2 (2000), 1617-1619; WO 02/10095) emerges in the stereoselective synthesis of cyanohydrins.
  • These mixtures should also be able to be produced in a comparatively simple manner, with good space-time yields and at reasonable cost, even in technical quantities, and should allow the use of cheap, also technically available, cyanide sources.
  • the radicals R, R 'and R "of the salen ligand of the general formulas (I) to (III) can be independently hydrogen, branched or unbranched C 1 -C 1 0 Aikylreste, in particular a methyl or tert-butyl radical, or a group O (CrC 4 alkyl), in particular a methoxy group or halogens, in particular Cl, an optionally substituted aryl group, in particular a phenyl group, or - (CH 2 ) m -, where m can be an integer between 1 and 8 ,
  • the mixtures contain the compounds of the formula VO m (Salen) n (I) in high proportions.
  • the compounds VO (salen) (II) and salen ligand (III) contained in the mixtures surprisingly do not have a negative effect on the catalytic activity, so that the mixtures can be used directly as a catalyst or catalyst component.
  • the present invention relates in particular to mixtures comprising 10 to 99.5, preferably 20 to 99.5, particularly preferably 50 to 99.5% by weight of the compound VOm (Salen) n (I), 0 to 90, preferably 0 to 80 , particularly preferably 0 to 50% by weight of the compound VO (salen) (II) and 0 to 50, preferably 0 to 35, particularly preferably 0 to 20% by weight of the compound (salen) (III).
  • a vanadyl (IV) salt for example vanadyl (IV) sulfate
  • a vanadyl (IV) salt is anhydrous or with water of hydration, with 1.4 to 10 equivalents, preferably with 1.4 to 5 Equivalents, in particular with 1.4 to 3 equivalents of the corresponding salen ligand reacted.
  • the compounds of the formulas (I), (II) and / or (III) containing vanadyl-salen complex mixtures are reacted in an organic solvent or organic-aqueous solvent mixtures.
  • Aliphatic or aromatic alcohols in particular in methanol, ethanol, 1-propanol or 2-propanol, or benzyl alcohol, in a heterogeneous reaction environment or in a chlorinated hydrocarbon / alcohol mixture, in particular in a mixture of dichloromethane, chloroform, dichloroethane, trichloroethane, chlorobenzene, are preferred ,
  • Dichlorobenzene, trichlorobenzene or chlorotoluene / alcohol or in an ether / alcohol mixture, in particular in a mixture of diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, diisobutyl ether, methyl tert-buty
  • the reaction takes place at a temperature of 0 to 120 ° C, preferably at 10 to 110 ° C, in particular at 20 to 100 ° C.
  • the salen ligand (III) is used in a concentration of 0.005 to 5.0 mol / l, preferably in a concentration of 0.009 to 2.5 mol / l, in particular in a concentration of 0.05 to 1.0 mol / l with respect to of the solvent.
  • the reaction time for the preparation of the catalysts is 1 to 24 h, preferably 2 to 16 h, in particular 3 to 10 h.
  • the component of formula (I) can be obtained by adding the vanadyl salen complex mixture in an organic solvent, e.g. Toluene, slurried and filtered.
  • the component with the formula (I) is found enriched or pure in the filter cake.
  • the components with the formulas (II) and (III) can be found enriched in the filtrate.
  • the vanadyl salen complex mixtures according to the invention are used for the production of optically active cyanohydrins of the formula (IV)
  • optically active center * has the absolute configuration (R) or (S)
  • R represents an optionally branched alkyl, alkenyl or alkynyl radical of the chain length Ci to C 20 or a radical of the formula (IVa)
  • X, Y and Z are independently the same or different and for H, F, Cl, Br, I, OH, NH 2 , O (-CC 4 alkyl), OCOCH 3 , NHCOCH 3 , NO 2 or CC 4th -Alkyl stand, by reacting an aldehyde of the formula (V)
  • R has the meaning given above, with a cyanide source in an organic solvent or in an organic-aqueous solvent mixture, at a temperature in the range from 0 to 60 ° C.
  • the vanadyl salen complex mixtures according to the invention are used by mixing the respective mixture with the aldehyde and a cyanide source in a suitable solvent.
  • 0.1 to 10 g of vanadyl salen complex mixture preferably 0.25 to 5 g of vanadyl salen complex mixture, in particular 0.3 to 3 g of vanadyl salen complex mixture, based on 1 mol of aldehyde used.
  • the reaction is carried out in the presence of the vanadyl-salen complex mixtures according to the invention, as already mentioned, at 0 to 60 ° C., in particular at 10 to 50 ° C., preferably at 20 to 40 ° C. In many cases it has proven useful to let the reaction proceed at room temperature.
  • a metal cyanide preferably an alkali metal cyanide, in particular sodium or potassium cyanide
  • the cyanohydrin of the formula (IV) contained in the reaction mixture can, if appropriate, be converted directly into the corresponding ⁇ -hydroxycarboxylic acid by hydrolysis.
  • the advantage of using the vanadyl-salen complex mixtures according to the invention is that it is possible not only to work the reaction of aldehydes in comparatively low-concentration amounts, for example 0.1 mol aldehyde / liter, but also the reaction with considerably higher aldehyde concentrations, for example 2.0 mol
  • Aldehyde / liter up to 10 mol aldehyde / liter, preferably 2 to 4 mol aldehyde / liter. Accordingly, the space-time yield for stereoselective cyanohydrin reactions is unusually high.
  • reaction with cyanide in the presence of the vanadyl salen complex mixtures according to the invention is carried out in an organic solvent or in an organic-aqueous solvent mixture.
  • organic solvents are C ⁇ CI O aromatic and C1-C10 aliphatic, optionally halogenated hydrocarbons or mixed solvents thereof, and aliphatic ethers having 1-5 carbon atoms per alkyl radical, or cyclic ethers having 4 - 5 carbon atoms in the ring.
  • aqueous solvent in addition to the organic solvent makes sense.
  • Water and aqueous solutions of acids are suitable as the aqueous solvent.
  • Aqueous solutions of mineral acids or of organic compounds with acidic functional groups, such as carboxylic acids, sulfonic acids and phosphonic acids, are particularly suitable.
  • Hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, citric acid or glutamic acid are particularly suitable.
  • the concentration of the acid in the aqueous solution is preferably 0 to 85%, in particular 0 to 60%.
  • an 85% acid concentration would correspond to the use of pure phosphoric acid, a 37% acid concentration to the use of concentrated hydrochloric acid.
  • Buffers are generally used to prepare 1% solutions.
  • the optically active cyanohydrin can be isolated from the reaction mixture and, if necessary, cleaned.
  • the optically active cyanohydrin e.g. crystallize in the cold, preferably at temperatures in the range from -20 ° C to 10 ° C.
  • the optically active cyanohydrin if appropriate in the form of the reaction mixture, can also be converted, for example by acid hydrolysis, into the corresponding optically active ⁇ -hydroxycarboxylic acid.
  • Strong acidic acids such as conc. HCI or aqueous sulfuric acid.
  • the aqueous phase, in which the acid is contained, and the organic phase, in which the optically active cyanohydrin is located, must be thoroughly mixed.
  • the vanadyl salen complex mixtures according to the invention make it possible, surprisingly, to convert aldehydes with high conversions and good ee values using a cyanide source at room temperature into the optically active cyanohydrins of both the (S) and the (R) series ,
  • an unexpectedly low catalyst / substrate ratio is necessary in order to obtain comparable conversions and ee values to previously known processes.
  • the presence of the salen ligand (III) in the Vanadyl-salen complex mixture which, when used in isolation, makes the cyanohydrin reaction completely non-selective, has no negative effects on the result of the stereoselective cyanohydrin reaction.
  • the efficient production of the vanadyl-salen complex mixture with an unexpectedly high space-time yield and easy cleaning makes it particularly economical to access one
  • Catalyst system for the production of optically active cyanohydrins found.
  • substrates which are particularly difficult, for example for enzymatic processes such as benzaldehydes substituted in the 2-position, for example 2-chlorobenzaldehyde, can also be used with good success using the vanadyl-salen complex mixture according to the invention, optionally with the corresponding optically active (S) - or Implement (R) cyanohydrins.
  • a mixture of salen ligands of the formula (III) and vanadium in the oxidation stage (IV), such as, for example, is prepared from vanadyl-salen complex mixtures in the examples below.
  • composition of the mixture by HPLC (% by weight): Component (I): (II):
  • the cyanohydrin reaction was carried out as described in Example 10, with 0.20 g of the vanadyl salen complex mixture prepared in Example 2, 31.8 g (0.30 mol) benzaldehyde, 15.0 g phosphate buffer (0.1 moiar; pH 4) and 20.2 g (0.75 mol) HCN in 150 ml toluene.
  • the turnover is 90%; 74% ee for the (S) -mandelic acid cyanohydrin.
  • the cyanohydrin reaction was carried out as described in Example 10, with 0.20 g of the vanadyl salen complex mixture prepared in Example 5, 31.8 g (0.30 mol) of benzaldehyde, 15.0 g of phosphate buffer (0, 1 molar; pH 4) and 20.2 g (0.75 mol) HCN in 150 ml toluene.
  • the turnover is 90%; 66% ee for the (S) -mandelic acid cyanohydrin.
  • the cyanohydrin reaction was carried out as described in Example 13, with 0.20 g of the vanadyl salen complex mixture prepared in Example 5, 42.5 g (0.30 mol) of 2-chlorobenzaldehyde, 15.0 g of phosphate buffer ( 0.1 molar; pH 4) and 20.2 g (0.75 mol) HCN in 150 ml toluene. According to the GC, the conversion is 99%; 72% ee for the (S) -2-chloromandelic acid cyanohydrin.

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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)

Abstract

L'invention concerne un mélange comprenant des complexes vanadyle-salen, contenant 10 à 99,9 % en poids d'un composé de formule VOm(Salen)n (I) dans laquelle m ? n et m < n, m = 1 et n = 2, et 0 à 90 % en poids d'un composé de formule VO(Salen) (II) et/ou 0 à 50 % en poids d'un ligand salen de formule (III), la somme de (II) et (III) ≠ 0, et les groupes R, R' et R'' du ligand salen de la formule générale (III) représentant indépendamment hydrogène, des radicaux alkyle C1-C10 linéaires ou ramifiés, ou un groupe O(alkyle C1-C4), ou F, Cl, Br ou I, un groupe aryle, éventuellement substitué, ou -(CH2)m-, m pouvant être un nombre entier compris entre 1 et 8 et n dans la formule (I) un nombre entier = 2.
PCT/EP2003/013635 2002-12-18 2003-12-03 Melanges contenant des complexes vanadyle-salen optiquement actifs WO2004055028A1 (fr)

Applications Claiming Priority (2)

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DE10259162.8 2002-12-18
DE2002159162 DE10259162A1 (de) 2002-12-18 2002-12-18 Optisch aktive Komplexe enthaltende Mischungen

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006032780A1 (fr) * 2004-09-21 2006-03-30 Centre National De La Recherche Scientifique (C.N.R.S) Complexes chiraux macrocycliques utilisables comme catalyseurs
EP2311800A1 (fr) * 2008-06-26 2011-04-20 Sumitomo Chemical Company, Limited Procédé de production d un composé à base de mandélonitrile

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10174879A (ja) * 1996-12-17 1998-06-30 Kagaku Gijutsu Shinko Jigyodan バナジウム錯体触媒
WO2002010095A2 (fr) * 2000-08-02 2002-02-07 King's College London, An Institution Incorporated By Royal Charter Procede de production de cyanhydrines a partir d'aldehydes
WO2003004157A2 (fr) * 2001-06-30 2003-01-16 Clariant Gmbh Catalyseurs optiquement actifs

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10174879A (ja) * 1996-12-17 1998-06-30 Kagaku Gijutsu Shinko Jigyodan バナジウム錯体触媒
WO2002010095A2 (fr) * 2000-08-02 2002-02-07 King's College London, An Institution Incorporated By Royal Charter Procede de production de cyanhydrines a partir d'aldehydes
WO2003004157A2 (fr) * 2001-06-30 2003-01-16 Clariant Gmbh Catalyseurs optiquement actifs

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
BELOKON' Y N ET AL: "Optimized catalysts for the asymmetric addition of trimethylsilyl cyanide to aldehydes and ketones", TETRAHEDRON, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, vol. 57, no. 4, 21 January 2001 (2001-01-21), pages 771 - 779, XP004314678, ISSN: 0040-4020 *
BELOKON Y N ET AL: "Vanadium-catalyzed asymmetric cyanohydrin synthesis", ORGANIC LETTERS, ACS, WASHINGTON, DC, US, vol. 2, no. 11, 2000, pages 1617 - 1619, XP002201072, ISSN: 1523-7060 *
LIU Z ET AL: "Electrochemical properties of vanadium(III,IV,V)-salen complexes in acetonitrile. Four-electron reduction of O2 by V(III)-salen.", INORGANIC CHEMISTRY. UNITED STATES 24 JAN 2000, vol. 39, no. 2, 24 January 2000 (2000-01-24), pages 274 - 280, XP002276986, ISSN: 0020-1669 *
NORTH M: "Synthesis and applications of non-racemic cyanohydrins", TETRAHEDRON: ASYMMETRY, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, vol. 14, no. 2, 17 January 2003 (2003-01-17), pages 147 - 176, XP004404175, ISSN: 0957-4166 *
PATENT ABSTRACTS OF JAPAN vol. 1998, no. 11 30 September 1998 (1998-09-30) *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006032780A1 (fr) * 2004-09-21 2006-03-30 Centre National De La Recherche Scientifique (C.N.R.S) Complexes chiraux macrocycliques utilisables comme catalyseurs
EP2311800A1 (fr) * 2008-06-26 2011-04-20 Sumitomo Chemical Company, Limited Procédé de production d un composé à base de mandélonitrile
EP2311800A4 (fr) * 2008-06-26 2014-06-04 Sumitomo Chemical Co Procédé de production d un composé à base de mandélonitrile

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