US20030166462A1 - Use of a solid hydrotalcite structure incorporating fluorides for basic catalysis of michael or knoevenagel reactions - Google Patents

Use of a solid hydrotalcite structure incorporating fluorides for basic catalysis of michael or knoevenagel reactions Download PDF

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US20030166462A1
US20030166462A1 US10/220,952 US22095203A US2003166462A1 US 20030166462 A1 US20030166462 A1 US 20030166462A1 US 22095203 A US22095203 A US 22095203A US 2003166462 A1 US2003166462 A1 US 2003166462A1
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solid
basic catalyst
anions
hydrotalcite
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Francois Figueras
Boyapati Choudary
Mannepalli Lakshimi Kantam
Vattipally Neeraja
Kottapalli Koteswara Rao
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Publication of US20030166462A1 publication Critical patent/US20030166462A1/en
Priority to US11/144,594 priority Critical patent/US7060859B2/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/007—Mixed salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
    • C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
    • C01F7/785—Hydrotalcite
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/02—Addition
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
    • 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
    • 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
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the present invention concerns basic catalysis reactions in organic chemistry.
  • the basic catalysts most often used in these reactions are typically strong liquid bases such as, for example, hydroxide, hydride and metallic alkoxide solutions used for homogeneous catalysis.
  • the first type of basic liquid catalysts suggested are a saturated solid support which includes microporous zeolites saturated by alkaline solutions, described amongst others by Hattaway et al. in the Journal of Catalysis, volume 119, page 497 (1982) or by Lasperas et al. in Microporous Materials, volume 1, page 343 (1993); alumina type supports saturated by potassium fluoride solutions (see also Clark et al., Chemical Review, volume 80, page 429 (1980).or by potassium nitrate solutions (refer to for instance, Yamaguchi et al., Chemical letters, page 989 (1997)).
  • heterogeneous solid catalysts one of the important parameters to be mastered is that of porosity of solids involved.
  • the pore size of solids used must be large enough to avoid heterogeneous catalysis inhibition linked to diffusion phenomena of species at the catalyst's surface.
  • the immobilisation of a liquid base on a support is not a very satisfactory solution: the saturated solid catalysts have the disadvantage of gradually deactivating as they are being used because of the dissolution of the active basic compound over time. This gradual dissolution may also take place due to the presence of reaction sub-products such as water and alcohol.
  • hydrotalcite In a stricter sense, by “hydrotalcite” one means magnesium and. aluminium hydrate basic carbonate (Mg6Al2(OH) 16CO3; 4H2O as described by Manasse et al., in Atti. Soc. Toscana Sc. Nat. Proc. Verb. Volume 24, page 92 (1915).
  • hydrotalcite designates a mixed carbonatized hydroxide demonstrating a lamellar structure with thin laminae similar to those of clay.
  • the basic structure of this solid, called “hydrotalcite structure” is that of magnesium hydroxide Mg (OH) 2 wherein some of the Mg2+ cations are replaced by A13+ cations possessing a molar ratio Mg/Al usually ranging from 1.5 to 4 and preferably to the order of 3.
  • Mg/Al magnesium hydroxide
  • an excess of charge due to the presence of A13+ ions is neutralised by the carbonate anions CO32. which play the role of compensating anions.
  • a hydrotalcite structure cannot show a molar ratio Mg/Al higher than 4.
  • the synthesis of this particular carbonatized mixed hydroxide has been described by Miyata et al. in Clays and Clay Minerals, volume 23, pages 369-375 (1975) and by Reichle et al. in Journal of Catalysis, volume 94, pages 547-557 (1985).
  • activated hydrotalcite one means, in relevance to the present invention, a compound obtained from physical, chemical and physicochemical treatment of hydrotalcite, possessing better catalysis properties to those of the initial hydrotalcite.
  • HDT a mixed magnesium and aluminium oxide
  • It has been described as an acceptable basic catalyst for aldolation reactions (refer to, for example, to the article by Suzuki et al. in the Bulletin of the Chemical Society of Japan, volume 61, pages 1008-1010 (1988)), for transesterification (refer to the Spanish patent SP 9601087 or to Corma et al.'s article in the Journal of Catalysis, volume 173, pages 315-321 (1998)), for Knoevenagel condensation reactions (see article by Climent et al. in the Journal of Catalysis, volume 151, pages 60-66 (1995)).
  • This mixed hydroxide “HDT-OH” is a Bronsted solid base with very interesting basic catalysis properties. Its use for aldolation of acetone has been described (refer to Catalysis of Organic Reactions by de Figueras et al., F. E. Herkes Edition, Marcel Dekker Inc., New York (1998), and for Knoevenagel condensations and Michael reactions (refer to article by Lakshmi Kantam et al., in Chemical Communications, volume 39, pages 1033-1034(1998)).
  • the “HDT-OH” catalyst thus obtained is an activated hydrotalcite with a basic structure of a hydrotalcite, wherein the carbonate compensating anions CO 3 2 ⁇ have been replaced by hydroxide anions OH.
  • OH ions present in the “HDT-OH” structure demonstrate an important unstable characteristic. In other words, exchangeable ions.
  • one of the objectives of this invention is to achieve heterogeneous basic catalysis of a Knoevenagel or Michael reaction with interesting yields.
  • the invention also has the intention of identifying activated hydrotalcite-like new solid basic catalysts that have a significant intrinsic basic character and which can replace advantageously the basic catalysts described in prior art
  • the objective of the present invention is the use of a solid basic catalyst with a hydrotalcite structure within which, at least a part of compensation anions are comprised of fluoride anions F for the basic catalysis of a Knoevenagel and Michael reaction.
  • the hydrotalcite structure of useful catalysts generally has a molar ratio Mg/Al ranging from 1.6 to 3.8.
  • the molar ratio Mg/Al characterising the hydrotalcite structure of useful catalysts is higher than 2, and preferably higher than 2.5. What is even better is that this ratio is higher than 2.6. Besides this molar ratio is less than 3.3. Thus, this ratio ranges between 2.5 and 3.8, preferably between 2.6 and 3.2 and most advantageously between 2.8 and 3.1. The ratio especially preferable would be 3.
  • the fluoride anions are specifically integrated to the compensation ions' state in the hydrotalcite structure. They are not supported simply by a solid support, as is the case of KF type saturated catalysts supported by alumina as described earlier.
  • the activated hydrotalcite of useful catalysts as per the invention will be designated below by the generic term—“HDT-F”. This in order to remind us that fluoride ion is present as compensation anions within the hydrotalcite structure.
  • the catalyst can moreover subsequently present a very small quantity of fluoride anions supported simply by the solid's surface.
  • the useful catalysts according to the invention preferably contain at least 0.5% as masse and advantageously at least 2.5% of fluoride ion masse. Whatever may be the content of fluoride ions, at least 95% preferably and at least 98% advantageously of fluoride ions present must be integrated to the compensation anion state within the “HDT-F” structure.
  • the catalysts useful according to the invention are advantageously found in the form of porous solids.
  • Their pore radius distribution is such that at least 50% of the pores have a mean diameter greater than 2 nm and preferably greater than 5 nm.
  • One of the advantages of the present invention is therefore to allow reactions involving more cumbersome solid support/substrata than those used with state-of-the-art basic catalysts.
  • the “HDT-F” catalysts useful according to the present invention behave like normal basic catalysts; for instance, like those with a strong hydroxide or hydride type base.
  • Knoevenagel condensation corresponds to the reaction of an aldehyde or a ketone on a compound possessing an activated methanol grouping which can be reflected in a schematic diagram by a global budget/balance:
  • the invention's catalysts are advantageously put to use to 0.01 g to 0.10 g per solid support/substrate millimole in order to obtain such yields.
  • the invention's catalysts because of their solid character can also be easily separated from products obtained at the end of the reaction.
  • the fluoride anions playing the role of compensation anions are sufficiently strongly linked to the solid's structure, the ‘HDT-F’ catalysts mostly possess enough stability to be recycled. This is an undoubted advantage vis a vis most other solid catalysts which have been described earlier.
  • the ‘HDT-F’ basic catalyst useful according to this invention and the solid basic catalysts in particular showing a hydrotalcite structure characterised by a Mg/Al ratio between 2.5 and 3.8 may be obtained by means of two main kinds of procedure.
  • One method for preparing a solid basic catalyst with a hydotalcite structure integrating fluoride anions as compensation anions is characterised by stages which:
  • the hydrotalcite structure solid of stage (1.1) may be obtained by any means known to person skilled in this art. However, to the extent that it is specifically meant for an exchange stage by fluoride ions, the hydrotalcite structure solid prepared during stage (1.1) is preferably a hydrotalcite structure compound where compensation anions are monovalent anions and preferably nitrate anions.
  • the hydrotalcite structure solid of stage (1.1 ) is therefore, generally obtained from an aqueous solution containing magnesium nitrate and alumina nitrate with an advantageous Mg/Al molar ratio ranging between 1.6 and 3.8.
  • the hydrotalcite structure solid of stage (1.1) shows a Mg/Al ratio between 2.5 and 3.8.
  • the Mg/Al ratio in the aqueous solution ranges between 2.5 and 3.8 preferably between 2.6 and 3.2: and, even more advantageously between 2.8 and 3.1.
  • this Mg/Al ratio could, for instance, be equal to 3.
  • the pH value of the solution is then adjusted to a value preferably between 8 and 10. This, in this case, gives us a coprecipitation of magnesium and alumina salts. One then obtains a hydrotalcite structure solid in an aqueous suspension form.
  • the solid obtained is then isolated from the medium, for instance, like by filtration.
  • the filtration stage is advantageously followed by a wet cleaning stage and a drying stage.
  • stage (1.1) of creating the hydrotalcite structure compound is generally advantageously carried out in atmosphere devoid of CO2, for instance under nitrogeneous atmosphere.
  • stage (1.2) of exchange by fluoride anions is on the other hand usually carried out by dispersion of the solid obtained at the end of stage (1.1) in an aqueous solution containing fluoride anions with a concentration preferably between 0.05 and 0.5 mol/l.
  • This solution is advantageously an aqueous solution including at least one fluoride salt easily soluble in water or preferably in a solution of potassium, ammonium, sodium, magnesium and/or cesium fluoride.
  • the fluoride ion solution used advantageously is also free of carbonate ions.
  • the anionic exchange reaction is a fairly quick reaction. It is usually carried out for a time period of 10 minutes to an hour and preferably for a time period of 20 to 30 minutes. Advantageously it is carried out under agitation.
  • the solid obtained at the end of stage (1.2) is then subjected to filtration generally followed by drying.
  • This operation is preferably undertaken in an atmosphere free of CO2, for instance under nitrogen atmosphere.
  • a second preparation method of a solid basic catalyst possessing a hydrotalcite structure and integrating fluoride anions as compensation anions, useful according to the invention, is characterised by stages which:
  • the mixed magnesium and aluminium oxide obtained at stage (11.1) is a solid possessing a structure called ‘HDT’ defined above and belongs to the oxide type described in the Journal of Catalysis, volume 173, pages 115-121 (1998).
  • the mixed oxide obtained at stage (11.1) is generally characterised by a Mg/Al molar ratio ranging from 1.6 to 3.8.
  • the mixed oxide of stage (11.1) is characterised specifically by a Mg/Al ratio ranging between 2.5 and 3.8, preferably between 2.6 and 3.2 and most advantageously between 2.8 and 3.1.
  • the ratio especially preferable would be 3.
  • the carbonated hydrotalcite structure solid used in the carbonate removal stage can be prepared according to a method described by Reichle et al. in the Journal of Catalysis, volume 94, pages 547-557 (1985).
  • the removal of carbonates forming a mixed oxide is generally carried out by calcining and advantageously at a temperature of 400° to 600° C.
  • the mixed oxide obtained at the end of stage (11.1) is usually cooled with nitrogen in the absence of CO2.
  • Stage (11.2) wherein the mixed oxide is hydrated reconstitutes the hydrotalcite structure.
  • this structure's reconstruction phenomenon from the oxide is a relatively slow process, limited especially by the diffusion speed of water within the solid. Therefore, the hydration stage (11.2) is often a lengthy stage taking usually 5 to 48 hours.
  • This hydration stage is moreover conducted specifically in the presence of fluoride ions. It is therefore generally carried out by dispersion of the solid obtained at the end of stage (11.1) in an aqueous solution containing an optimum of fluoride ions, advantageously an aqueous solution of potassium. ammonium, sodium, magnesium and/or cesium fluoride, at an advantageous concentration ranging from 0.05 to 0.5 mol/l. in such a manner as to introduce an optimum of fluoride ions within the structure.
  • the fluoride ion solution used is preferably free of carbonate ions.
  • this stage is carried out under agitation.
  • stage (11.2) the solid obtained at the end of stage (11.2) goes through a filtration stage which is usually followed by drying. These stages are conducted; it is preferable, in a nitrogenous atmosphere free of CO2.
  • the suspension obtained was heated to 338 K for 16 hours.
  • the precipitate then obtained was filtered, washed with warm distilled water until the filtration water pH was equal to 7.
  • the carbonatized hydrotalcite was then dried in a heat/steaming chamber at 353K during 15 hours.
  • the carbonatized hydrotalcite obtained at the end of the drying stage was given calcining heat treatment under airflow with an increase in temperature from 25° C. to 450° C. in order to remove carbonates from the hydrotalcite and to form a mixed oxide of HDT structure.
  • the mixed oxide has then been cooled under nitrogen to avoid recarbonation.
  • Table 2 hereunder, groups the results observed for different kinds of acceptors and donors.

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US10/220,952 2000-03-08 2001-03-06 Use of a solid hydrotalcite structure incorporating fluorides for basic catalysis of michael or knoevenagel reactions Abandoned US20030166462A1 (en)

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FR0002987A FR2806008B1 (fr) 2000-03-08 2000-03-08 Catalyseur solide de structure hydrotalcite integrant des ions fluorures
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004009549A1 (de) * 2004-02-24 2005-09-15 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Durchführung von basisch katalysierten Reaktionen
US20090275713A1 (en) * 2005-06-24 2009-11-05 Shah Pankaj V Method for promoting Michael addition reactions
US9248426B2 (en) 2012-02-02 2016-02-02 Samsung Electronics Co., Ltd. Adsorbent for carbon dioxide, method of preparing the same, and capture module for carbon dioxide
CN111282583A (zh) * 2020-02-19 2020-06-16 天津大学 一种掺氟水滑石材料负载金属基催化剂及制备方法及应用
CN116196222A (zh) * 2023-02-28 2023-06-02 上海沐良医疗器械有限公司 防龋齿添加剂、防龋齿材料、牙科膜片及隐形矫治器

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US7855262B2 (en) * 2005-05-17 2010-12-21 Sun Chemical Corporation Size selective catalysis with ion exchange resins
US9181505B2 (en) * 2009-06-03 2015-11-10 Texaco Inc. & Texaco Development Corporation Integrated biofuel process
CN101659620B (zh) * 2009-09-04 2012-12-12 浙江工业大学 一种2,5-二氨基甲苯的绿色合成方法
GB201015603D0 (en) * 2010-09-17 2010-10-27 Magnesium Elektron Ltd Inorganic oxides for co2 capture
CN105001085B (zh) * 2015-04-26 2017-03-01 衢州学院 一种用层状材料催化合成二氟乙酰乙酸乙酯的方法
US10287239B1 (en) 2018-05-16 2019-05-14 University Of Florida Research Foundation, Inc. Methods and compositions for terpenoid tricycloalkane synthesis

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US4458026A (en) * 1982-06-02 1984-07-03 Union Carbide Corporation Catalysts for aldol condensations
US5260495A (en) * 1991-08-23 1993-11-09 Union Carbide Chemicals & Plastics Technology Corporation Monoalkylene glycol production using highly selective monoalkylene glycol catalysts

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US5814291A (en) * 1996-07-19 1998-09-29 Aristech Chemical Corporation Simplified synthesis of anion intercalated hydrotalcites
ES2299538T3 (es) * 2001-03-07 2008-06-01 Firmenich Sa Procedimiento para la preparacion de aductos de michael.
US6812186B2 (en) * 2002-03-27 2004-11-02 Council of Industrial Research Preparation of new layered double hydroxides exchanged with diisopropylamide for C-C bond forming reactions

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US4458026A (en) * 1982-06-02 1984-07-03 Union Carbide Corporation Catalysts for aldol condensations
US5260495A (en) * 1991-08-23 1993-11-09 Union Carbide Chemicals & Plastics Technology Corporation Monoalkylene glycol production using highly selective monoalkylene glycol catalysts

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004009549A1 (de) * 2004-02-24 2005-09-15 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Durchführung von basisch katalysierten Reaktionen
DE102004009549B4 (de) * 2004-02-24 2005-12-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Durchführung von basisch katalysierten Reaktionen
US20090275713A1 (en) * 2005-06-24 2009-11-05 Shah Pankaj V Method for promoting Michael addition reactions
US7799943B2 (en) 2005-06-24 2010-09-21 Rohm And Haas Company Method for promoting Michael addition reactions
US9248426B2 (en) 2012-02-02 2016-02-02 Samsung Electronics Co., Ltd. Adsorbent for carbon dioxide, method of preparing the same, and capture module for carbon dioxide
CN111282583A (zh) * 2020-02-19 2020-06-16 天津大学 一种掺氟水滑石材料负载金属基催化剂及制备方法及应用
CN116196222A (zh) * 2023-02-28 2023-06-02 上海沐良医疗器械有限公司 防龋齿添加剂、防龋齿材料、牙科膜片及隐形矫治器

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FR2806008A1 (fr) 2001-09-14
DE10195885T1 (de) 2003-05-08
AU2001239347A1 (en) 2001-09-17

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