WO2016189548A1 - Procédé permettant la préparation d'époxydes d'aryloléfines cycliques et acycliques à l'aide de promoteurs organiques recyclables - Google Patents

Procédé permettant la préparation d'époxydes d'aryloléfines cycliques et acycliques à l'aide de promoteurs organiques recyclables Download PDF

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WO2016189548A1
WO2016189548A1 PCT/IN2016/050064 IN2016050064W WO2016189548A1 WO 2016189548 A1 WO2016189548 A1 WO 2016189548A1 IN 2016050064 W IN2016050064 W IN 2016050064W WO 2016189548 A1 WO2016189548 A1 WO 2016189548A1
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mol
reaction mixture
hydrogen peroxide
reaction
organic layer
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PCT/IN2016/050064
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English (en)
Inventor
Noor-Ul Hasan Khan
Rukhsana Ilyas Kureshy
Sayed Hasan Razi Abdi
Hari Chand Bajaj
Tamal ROY
Minaxi Samatbhai MARU
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Council Of Scientific & Industrial Research
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/28—Only halogen atoms, e.g. cyanuric chloride

Definitions

  • the present invention relates to synthesis and use of recyclable organic promoters in the preparation of epoxides of cyclic and acyclic aryl olefins using hydrogen peroxide as an oxidant.
  • the present invention involves the use of a recyclable organic promoter, an inorganic base and a metal salt as a catalyst for the synthesis of epoxides from alkenes viz., styrene, indene, 1,2-dihydronapthalene and chromenes in the presence of hydrogen peroxide as an oxidant.
  • the product epoxides obtained from the above olefins have their application in flavors, fragrance, agrochemicals and pharmaceuticals industry.
  • Epoxides of cyclic and acyclic aryl olefins are versatile intermediates in synthetic chemistry as stereospecific ring opening of these leads to compounds with industrial application.
  • the synthesis of epoxides from olefins is a second order reaction which produces lots of heat during the course of the reaction which needs to be taken care of to avoid over-oxidized and thermal -degraded side products.
  • epoxides from olefins gathers lots of attention from the industry and is a process of great economic significance.
  • epoxides are formed from alkenes in the presence of an oxygen donor with often involvement of an external catalyst.
  • oxidizing agents such as commercial bleach, organic hydroperoxides, organic per acids, iodosyl arines, oxones, molecular oxygen (in the form of pure oxygen or air) and hydrogen peroxide have been used for production of epoxides from alkene.
  • Transition metal salts or complexes have been used as catalyst for alkene epoxidation with aqueous H 2 O 2 (E. N. Jacobsen, In Comprehensive Organometallic Chemistry II; E. W. Abel, F. G. Stone, E. Wilkinson, Eds. Pergamon: New York, 1995. Vol. 12 p. 1097; H. R. Tetzlaff, J. H. Espenson, Inorg. Chem. 38 (1999) 881).
  • Other methods for activation of H 2 O 2 include forming reactive peroxy acids from carboxylic acids (D. Swern , In Organic peroxides; D. Swern Eds. Wiley Interscience, New York 1971 Vol. 2 p.
  • Peroxymonocarbonate is an anionic peracid and is a potent oxidant in aqueous solution. Similarly nitriles have also been shown to activate hydrogen peroxide via in-situ production of potent epoxidising reagent-peroxyimidic acids in alkaline media (in general known as Payne system; G. B. Payne et al, J. Org. Chem. 26 (1961) 659; G. B. Payne, Tetrahedron 18 (1962) 763).
  • EP2, 123,645 (2008) discloses a process for epoxidation of olefins that comprised of reacting an olefin with a mixture obtained by mixing an acid anhydride and urea peroxide in an appropriate solvent.
  • the drawback associated with this process is the use of a corrosive anhydride which was not safe.
  • the main object of the present invention is to provide an improved process for the synthesis of epoxides from olefins using a recyclable organic promoter.
  • Another object of the present invention is to provide an improved process of aryl alkene epoxidation using an inorganic base, a metal salt as a catalyst, a recyclable organic promoter in the absence or presence of an organic solvent at a reaction temperature of 10-30 °C and time of4-12h.
  • Yet another object of the present invention is to utilize a metal source as a catalyst and to produce styrene oxide from styrene in >95% yield and >96% selectivity in absence of an organic solvent.
  • present invention provides a process for the preparation of epoxides from alkenes comprising the steps of:
  • step (i) continuous stirring the mixture as obtained in step (i) with 50% hydrogen peroxide for period in the range of 2 to 10 hr followed by filtering and separating the reaction mixture by layer separation method to obtain aqueous layer and organic layer;
  • alkenes used are selected from the group consisting of substituted or unsubstituted styrene, indene, 1,2-dihydronaphthalene and substituted or unsubstituted chromones.
  • transition metal salt used is selected from the group consisting of cobalt, manganese, nickel, copper, iron, chromium and vanadium and the counter ion is selected from the group consisting of chloride, bromide, iodide, carbonate, bicarbonate, perchlorate, sulphate, nitrate, acetate or phosphate.
  • the inorganic base used is selected from the group consisting of carbonates and bicarbonates of alkali metals selected from lithium, sodium, potassium and cesium.
  • concentration of the promoter used is in the range of 0.003 mol to 4.0 mol.
  • the organic promoter is recovered by simple filtration from the reaction mass.
  • the temperature of the reaction is maintained in the range of -10 to 80 °C.
  • the aging period of the reaction mixture is maintained in the range of 3 to 15 h.
  • present invention provides a process for the preparation of organic promoter comprising the steps of:
  • step (i) heating the powder as obtained in step (i) at 3-7 °C/min rate till it reaches 140 to 150 °C followed by keeping at 140 to 150 °C for 5 to 6 hours to obtain solid mass;
  • step (iii) cooling the solid mass as obtained in step (ii) at room temperature in the range of 25 to 30°C followed by washing , drying at 25 to 30 °C under vacuum to obtain organic promoter.
  • amino compounds used are selected from the group consisting of urea, thiourea, ⁇ , ⁇ -dimethylurea, ethylenediamine, o- phenylenediamine, m-phenylenediamine, p-phenylenediamine, trans- 1,2-diamimo cyclohexane
  • epoxidation reactions may be conducted under triphasic conditions in the absence of an organic solvent.
  • the contemporary invention divulges the catalytic oxidative process for the conversion of alkenes to their corresponding epoxides.
  • Present invention provides an improved process for the synthesis of epoxides from olefins using a recyclable organic promoter which comprises of reacting an olefin with a system composed of an inorganic base, a recyclable organic promoter in the presence of a transition metal salt catalyst and hydrogen peroxide as an oxidant under triphasic heterogeneous system. After separation of the heterogeneous organic promoter by filtration or centrifugation, the resulting epoxide is separated from the aqueous layer by layer separation method or by solvent extraction method depending on the nature of the epoxide.
  • the process comprises the reaction of alkenes with oxygen atom in the existence of the inorganic salts and specific organic co-promoter to produce the epoxide yields under the suitable catalytic conversion condition.
  • the laboratory scale reaction was done with the laboratory reagent grade alkenes as a substrate in 250 ml two necked round bottom flask set on the stirring device and fitted with an efficient water condenser by keeping 20 °C temperature of the reaction mass with continuous stirring to yield the analogous epoxides from the alkenes.
  • slow addition of hydrogen peroxide was required to form in situ highly active peroxo intermediate species, which is key point for the formation of epoxide.
  • the catalytic oxidation of alkenes proceeds through the following reaction scheme.
  • the present invention of epoxidation reaction encompasses the triphasic homogeneous system by the combination of both, inorganic and recyclable organic promoters.
  • concentration range of alkene used in the present invention was 0.007 to 15 mol, from which, 0.01 to 10 mol concentration range was preferred for catalytic conversion of alkene to epoxide by using hydrogen peroxide as an oxidant at a moderate temperature and atmospheric pressure.
  • the alkene concentration was in the range of 0.1 to 0.8 mol in combination with inorganic promoter in the range of 0.033 to 0.1 mol and recyclable organic co-promoter in the range of 20 to 50 g with respect to alkene, greater yield conversion of alkene oxide was obtained.
  • the alkene oxide product was extracted from the reaction mass and characterized by GC and 3 ⁇ 4 NMR.
  • the catalytic conversion of the alkenes to their epoxides proceeds through normal temperature and atmospheric pressure of solvent, which is water in the present disclosure.
  • solvent which is water in the present disclosure.
  • the catalytic conversion of alkenes to their respective epoxides is very slow, between 35 to 40 % even after 8 h.
  • Increase of the temperature ploddingly to 50 °C helps for the achievement of the complete conversion of alkenes to their resultant epoxides in lower reaction time.
  • the transition metal salt plays a very crucial role for the electrophilic activation of alkenes; therefore the metal salts may be added to the reaction mixture in the concentration range of 0.011 mol to 0.05 mol. Less than 15 % conversion of epoxide obtains with a very small quantity of metal salts which sloths the catalytic reaction during the epoxidation process, hence the ideal quantity of transition metal salts is required for the essential catalytic transformation.
  • the addition period of hydrogen peroxide is important followed by the aging of the reaction to achieve higher yields and conversion of epoxide. Decrease the time period of addition of hydrogen peroxide less than 2 hour followed by aging of the reaction less than 4 hour resulted in poor conversion of alkene to epoxide. No improvement has occurred by increasing the time of addition and subsequent aging period beyond 6 h and 15 h respectively.
  • the time may be varied in the range of 2 to 10 h, especially in the range of 3 to 6 h followed by aging in the range of 2 to 20 h preferably in the range of 3 to 15 h.
  • the concentration of hydrogen peroxide used may vary in the range of 5 to 55%, appropriately in the range of 10 to 50 % for obtaining higher oxygen atom efficiency with respect to the alkenes.
  • the optimal quantity of transition metal salt is essential accompanied by the hydrogen peroxide as it tends to decompose hydrogen peroxide later on too.
  • a combination of metal salts with hydrogen peroxide forms a highly active peroxo intermediate species, which enhances the conversion of alkenes to epoxides.
  • the preparation of alkene oxides throughout the present invention is suitable for wide variety of applications of epoxides.
  • the epoxidation reaction was affected by the use of transition metal salts as a catalyst in combination with an inorganic base and an organic solvent wherein the conversion and selectivity of epoxides were higher than those of reported in past literature.
  • the reaction method of the present invention does not have need of any special device and the use of hazardous and corrosive chlorine gas is dispensed.
  • the catalytic procedure for the preparation of epoxides from alkene gives oxides having high purity yields in absence of organic solvents at moderate temperature.
  • the inventive steps adopted in the presence invention are:
  • the efficient organic co -promoter is used in the catalytic epoxidation of the alkene with great recyclability.
  • the epoxidation reaction does not require higher temperature and pressure; it is carried out at a low temperature and atmospheric pressure.
  • the process is eco-benign.
  • the epoxidation reaction is affected using inexpensive transition metal salt as a catalyst and the need for expensive tungstic acid, complexes of molybdic acid and silver containing catalyst is dispensed.
  • reaction vessel In a typical catalytic course of reaction, the appropriate transition metal salt, alkene, inorganic salt and recyclable organic additive in water was taken in a reaction vessel at a required temperature. The oxidant was added at a defined rate and after completion of reaction epoxide was separated in a separating funnel by using suitable non-halogen solvents and purified by distillation or crystallization as the case may be. The purity of the product was determined by Gas Chromatography and 3 ⁇ 4 NMR.
  • EXAMPLE 5 A mixture of cyanuric chloride (10 g; 0.05 mol) and thiourea (22.83 g; 0.3 mol) was finely grinded in a mortar with the help of a pestle at 28 °C. The powder thus obtained was transferred to a glass vessel which was heated at 5 °C/min rate till it reaches 150 °C. The reaction mixture was kept at 150 °C for 6 hours. Thereafter the resulting solid mass was allowed to cool to room temperature (28 °C) and washed with water (50 mL x 3) followed by acetone (50 mL x 3) and dried at 30 °C under vacuum to give a white solid hereafter referred as TAP-5. Yield: 9.87 g; 59.96 %. Melting point: >200 °C.
  • the cyanuric chloride (10 g; 0.05 mol) and ethylenediamine (20 mL; 0.3 mol) was mixed thoroughly at 28 °C in a glass vessel which was then heated at 5 °C/min rate till it reaches 150 °C.
  • the reaction mixture was kept at 150 °C for 6 hours. Thereafter the resulting solid mass was allowed to cool to room temperature (28 °C) and washed with water (50 mL x 3) followed by acetone (50 mL x 3) and dried at 30 °C under vacuum to give a white solid hereafter referred as TAP-7.
  • the cyanuric chloride (10 g; 0.05 mol) and trans- 1,2-diamimo cyclohexane (36.22 mL; 0.3 mol) was mixed thoroughly at 28 °C in a glass vessel which was then heated at 5 °C/min rate till it reaches 150 °C.
  • the reaction mixture was kept at 150 °C for 6 hours. Thereafter the resulting solid mass was allowed to cool to room temperature (28 °C) and washed with water (50 mL x 3) followed by acetone (50 mL x 3) and dried at 30 °C under vacuum to give a white solid hereafter referred as TAP-11. Yield: 15.86 g; 69.92 %. Melting point: >200 °C
  • the aqueous layer was extracted with 4 x 20 mL diethyl ether.
  • the combined organic layer was distilled to yield styrene oxide.
  • the conversion to epoxide is 92.66 % with 92.66 % selectivity.
  • Organic ligand based metal complexes are not required for the activation of hydrogen peroxide and alkenes under the reaction conditions used in the present invention.
  • Epoxidation reactions are run under aerobic condition and no prior oxygen free conditions are required.
  • Organic promoter used for the reaction can be separated out from the reaction mass just by filtration or centrifugation hence minimizing the waste to a significant extent.
  • Organic promoter used in this reaction is highly recyclable and could be reused for more than 10 cycles without any loss in its activity.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Compounds (AREA)

Abstract

La présente invention concerne l'époxydation d'alcènes c'est-à-dire, de styrène, d'indène, de 1,2-dihydronaphtalène et de chromènes à l'aide de promoteur organique recyclable en présence d'une base minérale et d'un sel métallique comme catalyseur avec du peroxyde d'hydrogène comme oxydant, pour produire des époxydes d'alcène à un rendement (95 %) et une sélectivité (96 %) élevés en l'absence de tout solvant organique. Promoteur organique recyclable représenté par la formule (1).
PCT/IN2016/050064 2015-05-27 2016-02-24 Procédé permettant la préparation d'époxydes d'aryloléfines cycliques et acycliques à l'aide de promoteurs organiques recyclables WO2016189548A1 (fr)

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IN1519DE2015 2015-05-27
IN1519/DEL/2015 2015-05-27

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050222440A1 (en) * 2004-03-31 2005-10-06 Khan Noor-Ul H Catalytic process for the preparation of epoxides from alkenes
WO2005095370A1 (fr) * 2004-03-31 2005-10-13 Council Of Scientific & Industrial Research Procede catalytique ameliore pour la preparation d'epoxydes a partir d'alcenes
US7169945B2 (en) 2002-11-26 2007-01-30 Degussa Ag Process for the epoxidation of olefins
EP1841753A1 (fr) 2005-01-18 2007-10-10 Basf Aktiengesellschaft Procede d'epoxydation d'une olefine a bilan energetique ameliore
US7345182B2 (en) 2005-12-27 2008-03-18 Central Salt And Marine Chemicals Research Institute Catalytic epoxidation of styrene with molecular oxygen using metal ion exchanged zeolites
US7482478B2 (en) 2004-03-18 2009-01-27 The University Of Hong Kong Diastereoselective epoxidation of allylically substituted alkenes using metalloporphyrin catalysts
EP2123645A1 (fr) 2007-02-22 2009-11-25 Adeka Corporation Composition d'agent oxydant pour l'époxydation d'oléfines et procédé pour l'époxydation des oléfines
WO2011062608A2 (fr) 2009-11-19 2011-05-26 Dow Global Technologies, Inc. Epoxydation d'une oléfine
US7981951B2 (en) 2006-06-23 2011-07-19 Dow Global Technologies Llc Process for producing epoxides from olefinic compounds
WO2011095296A1 (fr) 2010-02-02 2011-08-11 Momentive Specialty Chemicals Research S.A. Procédé d'époxydation
US8080677B2 (en) 2005-10-25 2011-12-20 University Of Kansas Process for selective oxidation of olefins to epoxides

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7169945B2 (en) 2002-11-26 2007-01-30 Degussa Ag Process for the epoxidation of olefins
US7482478B2 (en) 2004-03-18 2009-01-27 The University Of Hong Kong Diastereoselective epoxidation of allylically substituted alkenes using metalloporphyrin catalysts
US20050222440A1 (en) * 2004-03-31 2005-10-06 Khan Noor-Ul H Catalytic process for the preparation of epoxides from alkenes
WO2005095370A1 (fr) * 2004-03-31 2005-10-13 Council Of Scientific & Industrial Research Procede catalytique ameliore pour la preparation d'epoxydes a partir d'alcenes
US7235676B2 (en) 2004-03-31 2007-06-26 Council Of Scientific & Industrial Research Catalytic process for the preparation of epoxides from alkenes
EP1841753A1 (fr) 2005-01-18 2007-10-10 Basf Aktiengesellschaft Procede d'epoxydation d'une olefine a bilan energetique ameliore
US8080677B2 (en) 2005-10-25 2011-12-20 University Of Kansas Process for selective oxidation of olefins to epoxides
US7345182B2 (en) 2005-12-27 2008-03-18 Central Salt And Marine Chemicals Research Institute Catalytic epoxidation of styrene with molecular oxygen using metal ion exchanged zeolites
US7981951B2 (en) 2006-06-23 2011-07-19 Dow Global Technologies Llc Process for producing epoxides from olefinic compounds
EP2123645A1 (fr) 2007-02-22 2009-11-25 Adeka Corporation Composition d'agent oxydant pour l'époxydation d'oléfines et procédé pour l'époxydation des oléfines
WO2011062608A2 (fr) 2009-11-19 2011-05-26 Dow Global Technologies, Inc. Epoxydation d'une oléfine
WO2011095296A1 (fr) 2010-02-02 2011-08-11 Momentive Specialty Chemicals Research S.A. Procédé d'époxydation

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