EP1732910A1 - Procede catalytique ameliore pour la preparation d'epoxydes a partir d'alcenes - Google Patents

Procede catalytique ameliore pour la preparation d'epoxydes a partir d'alcenes

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Publication number
EP1732910A1
EP1732910A1 EP04769734A EP04769734A EP1732910A1 EP 1732910 A1 EP1732910 A1 EP 1732910A1 EP 04769734 A EP04769734 A EP 04769734A EP 04769734 A EP04769734 A EP 04769734A EP 1732910 A1 EP1732910 A1 EP 1732910A1
Authority
EP
European Patent Office
Prior art keywords
mol
alkenes
catalytic process
improved catalytic
epoxides
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Withdrawn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
EP04769734A
Other languages
German (de)
English (en)
Inventor
N.H. Central Salt&Marine Chemicals Res.Inst. KHAN
S.H.R. Central Salt&Marine Chemicals Res.Inst ABDI
R.I Central Salt&Marine Chemicals Res.Inst KURESHY
S. Central Salt&Marine ChemicalsRes.Inst. SINGH
I. Central Salt&Marine Chemicals Res.Inst. AHMED
R.V. Central Salt&Marine Chemicals Res.Inst. JASRA
P.K. Central Salt&Marine Chemicals Res.Inst. GHOSH
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.)
Council of Scientific and Industrial Research CSIR
Original Assignee
Council of Scientific and Industrial Research CSIR
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
Priority claimed from US10/823,318 external-priority patent/US7235676B2/en
Application filed by Council of Scientific and Industrial Research CSIR filed Critical Council of Scientific and Industrial Research CSIR
Publication of EP1732910A1 publication Critical patent/EP1732910A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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

Definitions

  • the present invention relates to an improved catalytic process for 1 the preparation of epoxides from alkenes. More particularly this invention relates to the use of transition metal salt in combination with inorganic base and an organic compound in the presence of hydrogen peroxide from alkene viz. styrene, indene, cyclohexene, 1,2- dihydronaphthalene, isoprene, ⁇ -pinene, 1-hexene, 1-octene, t-4-octene.
  • transition metal salt in combination with inorganic base and an organic compound in the presence of hydrogen peroxide from alkene viz. styrene, indene, cyclohexene, 1,2- dihydronaphthalene, isoprene, ⁇ -pinene, 1-hexene, 1-octene, t-4-octene.
  • Epoxides are highly reactive chemical compounds which as a result of their reactivity, can be used in a wide variety of application. Epoxidation is a second-order and is highly exothermic reaction with heat of reaction (ca. 250 kJ/mol); therefore care must be taken
  • epoxides by the oxidation of alkenes
  • epoxides are formed by the reaction of an alkene with an oxidizing agent in the presence of a catalyst.
  • oxidizing agents such as commercial bleach, organic hydroperoxides, organic per acids, iodosyl arines, oxones, molecular oxygen (in the fo ⁇ n of pure oxygen or atmospheric oxygen) and hydrogen peroxide have been used to prepare a variety of alkene epoxides.
  • Hydrogen peroxide is a high oxygen content, environmentally friendly oxidant for which water is the sole by-product in heterolytic oxidation, but it is a slow oxidant in absence of activation due to the poor-leaving tendency of the hydroxide ion.
  • G. Strukul Catalytic Oxidation with Hydrogen Peroxide as oxidant: Kluwer: Dordrecht 1992 and j. O. Edwards, In Peroxide Reaction Mechanism; O. J. Edward, Ed. h terscience: New York, 1962; pp, 67).
  • 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.
  • H 2 O reactive peroxy acids from carboxylic acids
  • D. Swern In Organic peroxides; D. Swern Eds. Wiley Interscience, New York 1971 Vol. 2 p. 355
  • peroxycarboximidic acid from acetdnitijijle
  • of peroxyiirea G. Majetich, R. Hicks, Synlett. (1996) 694
  • perborate or sodium percarbonate in strongly basic solution A. McKillop, W. R. Sanderson, Terahedron, 51 (1995) 6145.
  • 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)1659; G. B. Payne, Tetrahedron 18 (1962) 763).
  • reaction effluent comprises by weight 58% propene, 4.6% propene oxide, 10.8% methyl benzyl alcohol, 18.2% ethyl benzene, 8.4% others.
  • the process has the following disadvantages, (i) it produces a low-cost alcohol as a by-product in an amount chemically equivalent to the epoxidised compound formed; ii) selectivity of the process is poor as it lead to the formation of unidentified products to the tune of nearly 18% by weight; iii) the catalyst deactivates after first run and need to regenerated; iv) the method is not suitable for higher and aromatic alkenes.
  • 5,155,241 (1992) have disclosed the preparation of styrene oxide by reacting styrene and hydrogen peroxide in heterogeneous system in . the presence of a bis (tri-n- alkyltinoxy)molybdic acid with an ar ⁇ ine and an inorganic anion respectively using 60% hydrogen peroxide as a source of oxygen which took 24 hours to give 77-82 % yield with 90% epoxide selectivity at 24° C in presence of a water insoluble solvent like chloroform, dichloroethane, benzene and acetonitrile.
  • a water insoluble solvent like chloroform, dichloroethane, benzene and acetonitrile.
  • the system has following disadvantages i) amount of buffered H 2 O 2 (10 equivalent) is appreciably large to obtain the high conversions thus oxygen atom efficiency for hydrogen peroxide is poor and require to handle very large volumes making the process not viable at commercial level; ii) it takes extended time period (16 h) to add the buffered H 2 O 2 as the reaction is highly exothermic under these reaction conditions.
  • G. Majetich et al. in Synlett (1996) 649 have described acidic/base carbodiimide- promoted epoxidation of 3-phenyl 1 -propene, cyclic and long chain alkenes, wherein carbodiimide in presence of hyrogen peroxide generates in situ peroxyisourea as the oxidant.
  • the main object of the present invention is to provide An improved catalytic process for the preparation of epoxides from alkenes which obviates the drawbacks as detailed above.
  • Another object of the present invention is to provide an improved process of alkene epoxidation using an inorganic promoter and an organic additive in the absence of an organic solvent or in the presence of a solvent using hydrogen peroxide as oxidant at moderate temperature in 2-7 h.
  • Yet another object of the present invention is to provide the catalytic activity of the transition metal salt in an organic solvent free reaction condition to obtained epoxide conversion of >99% and epoxide selectivity in the range of 95 to 97%.
  • Yet another object of the present invention is to provide a catalytic processes using I transition metal salt for epoxidation of alkenes under moderate condition of temperature and pressure.
  • Yet another object of the present invention is to develop a catalytic process for epoxidation of alkene using H 2 O 2 as an oxidant.
  • Still another object of the present invention is to achieve epoxide conversion, even in absence of transition metal salt.
  • the present invention relates to an improved catalytic process for the preparation of epoxides from alkenes. More particularly this invention relates to the use of transition metal salt in combination with inorganic base and an organic compound in the presence of hydrogen peroxide from alkene viz. styrene, indene, 'jjicyclohexene, 1,2- dihydronaphthalene, isoprene, -pinene, 1-hexene, 1-octene,! t-4- ⁇ ctelle.
  • transition metal salt in combination with inorganic base and an organic compound in the presence of hydrogen peroxide from alkene viz. styrene, indene, 'jjicyclohexene, 1,2- dihydronaphthalene, isoprene, -pinene, 1-hexene, 1-octene,! t-4- ⁇ ctelle.
  • the present invention provides An improved catalytic process for the preparation of epoxides from alkenes which comprises reacting an alkenes in a concentration range of 0.00-1 mol to 10 mol in presence or in absence of a transition metal salt in a concentration range of 0.01 mmol to 0.01 mol combination with an inorganic base in a concentration range of 0.0003 mol to 4.0 mol and an organic compound in. a concentration range 0.02 mol to 30.0 mol as catalyst under biphasic homogeneous system
  • the alkenes used may be selecte from styrene, indene, cyclohexene, 1,2-dihydronaphthalene, isoprene, ⁇ -pinene, 1-hexene, 1- octene and t-4-octene.
  • transition metal salt wherein the transition metal may be cobalt, manganese, nickel, copper, iron, chromium and vanadium while the counter ion like chloride, bromide, iodide, carbonate, bi-carbonate, perchlorate, sulphate, nitrate, acetate, phosphate.
  • epoxidation reactions may be conducted under biphasic conditions in the absence of an organic solvent or in the presence of a solvent that may be selected from benzene, flurobenzene, chlorobenzene, nitrobenzene, 1,4-dioxane acetonitrile, benzonitrile, formamide, acetkmide, propamide, l ,
  • the inorganic promoter may be carbonates and bicarbonates of alkali metals like lithium, sodium, potassium and cesium.
  • an organic additive may be nitriles e.g. acetonitrile and benzonitrile, amides e.g. formamide, acetamide, propamide, dimethylformamide, dimethylacetamide, urea, alkyl substituted urea, aryl substituted
  • the reaction was conducted on laboratory scale in 250 ml two-necked round bottom flask fitted with an efficient water condenser. Laboratory reagent grade alkenes were used as a substrate. The catalytic conversion was carried out in presence of inorganic salts and organic co-promoter. Highly active per oxo intermediate species, was generated in situ by slow addition of hydrogen peroxide required for epoxidation. The reaction mixture was allowed to age at 20°C with constant stirring to yield the respective epoxides.
  • the process according to the present invention was carried ; o ⁇ t by using, alkene concentration in the range of 0.007 to 15 mol, preferably in the range, of 0.01 to lOmol by ⁇ I' catalytic conversion using H 2 O as oxidant at a moderate tempefatu ⁇ p'and atmospheric pressure.
  • the epoxidation reaction was carried out in combination 'with inorganic and organic promoters under biphasic homogeneous system. Higher yields of alkene epoxides were obtained when the alkene concentration was more than 0.1 mol in combination with (i) inorganic promoter in the range of 0.0003 mol to 4 mol and (ii) organic co-promoter in the range of 0.02 mol to 30 mol.
  • the product, alkene oxide was extracted, distilled and characterised by GLC and 1H NMR.
  • the temperature of the reaction mixture may be maintained in the temperature range of -10 to 110 °C, preferably in the range of -5 to 75 °C.
  • the catalytic reaction proceeds through the catalytic oxidation at. normal to boiling temperature of solvents used and atmospheric pressure. At temperature below -5 °C the catalytic conversion is very slow and the respective oxides obtained after 6 h was only 40%). Gradual increase of the temperature to ca 70°C helps in achieving the complete conversion of alkenes to their respective epoxides.
  • the transition metal salt plays a very vital role in activating the alkenes.
  • the metal salts may be added to the reaction mixture in the concentration range of 0.007 mol to 0.02 mol, preferably in the range of 0.01 m ol to
  • the time required for the' addition of hydrogen peroxide followed by aging of the reaction are critical in achieving higher yields and conversion.
  • the time of addition maybe varied in the range of 1 to 10 h, preferably in the range of 2 to 6 h followed by aging in the range of 2 to 20 h preferably in the range of 3 to 15 h. It was observed that decreasing the time of addition below 1 h followed by aging less than 2 h resulted in lower conversion of alkene to epoxide.
  • the concentration of oxidant may be varied in the range of 5 to 55%, preferably in the range of 10 to 50% for obtaining higher oxygen atom efficiency with respect to the substrate (alkenes).
  • the optimum quantity metal salt is essential, as the later also tends to decompose hydrogen peroxide. This may result in the need 'of higher quantity of hydrogen peroxide, which may adversely effect the economies' ' of the process.
  • a combination of metal salts with hydrogen peroxide forms a highly active ⁇ peroxo intermediate species, which enhances the conversion of alkenes to epoxides.
  • the present invention relates to the preparation of alkene oxides suitable for various applications.
  • These alkene oxides were prepared from a wide range of alkenes by catalytic conversion using hydrogen peroxide as oxidant at moderate temperature and atmospheric pressure.
  • the epoxidation reaction was affected by the use of transition metal salts as catalyst in combination with inorganic base and an organic solvent wherein process for the preparation of epoxides from alkene in presence and absence of organic solvents and at moderate temperature, yield oxide having high purity.
  • the inventive steps adopted in the presence invention are (i) commercial hydrogen peroxide is used as oxidant for the epoxidation of alkenes and the use of chlorine gas as oxidant is dispensed; (ii) the epoxidation reaction is carried out at lower temperature and atmospheric pressure and does not require higher temperature and pressure; (iii) the epoxidation reaction obviates the need of anhydrous condition and the catalytic conversion takes place in organic and/or aqueous medium; (iv) for most alkenes organic solvent is not needed for the epoxidation reaction to occur, thus makes the process eco-benign, however where ever solvent is required, the same does not form explosive mixt ⁇ re with molecular
  • EXAMPLE 1 To a mechanically stirred solution of styrene (0.1 mol), dodecane (O.Olmol), urea (2.08 mol), sodium bicarbonate (0.03 mol) and manganese sulphate (0.0001 mol) in 50.0 ml of water at 20°C is added 30% aqueous hydrogen peroxide (0.22 mol). drop-wise over a period of 4 h. After 4.5 h the organic layer of the reaction mixturejiwas separated by a separating funnel. The aqueous layer was extracted with 4 x 20 mLidiethyl ether. The combined organic layer was distilled to yield styrene oxide. The- conversion to epoxide is 99% with 94% selectivity. EXAMPLE 2
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé catalytique amélioré pour la préparation d'époxydes à partir d'alcènes, à l'aide d'une combinaison de sel de métal de transition, d'un promoteur inorganique et d'un additif organique en l'absence de solvant ou en présence d'un solvant avec du peroxyde d'hydrogène disponible dans le commerce. Ainsi, de l'oxyde de styrène est préparé à l'échelle du kilogramme avec un rendement isolé de 86 % et une pureté supérieure à 95 %.
EP04769734A 2004-04-13 2004-10-27 Procede catalytique ameliore pour la preparation d'epoxydes a partir d'alcenes Withdrawn EP1732910A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/823,318 US7235676B2 (en) 2004-03-31 2004-04-13 Catalytic process for the preparation of epoxides from alkenes
PCT/IB2004/003512 WO2005095370A1 (fr) 2004-03-31 2004-10-27 Procede catalytique ameliore pour la preparation d'epoxydes a partir d'alcenes

Publications (1)

Publication Number Publication Date
EP1732910A1 true EP1732910A1 (fr) 2006-12-20

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EP04769734A Withdrawn EP1732910A1 (fr) 2004-04-13 2004-10-27 Procede catalytique ameliore pour la preparation d'epoxydes a partir d'alcenes

Country Status (5)

Country Link
EP (1) EP1732910A1 (fr)
JP (1) JP4733109B2 (fr)
KR (1) KR101131207B1 (fr)
CN (1) CN1926124B (fr)
WO (1) WO2005095370A1 (fr)

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EP2103604A1 (fr) 2008-03-17 2009-09-23 Evonik Degussa GmbH Procédé de fabrication d'épichlorhydrine
EP2149570A1 (fr) 2008-08-01 2010-02-03 Hexion Specialty Chemicals Research Belgium S.A. Procédé de fabrication d'épichlorhydrine avec peroxyde d'hydrogène et un complexe manganèse
EP2149569A1 (fr) 2008-08-01 2010-02-03 Hexion Specialty Chemicals Research Belgium S.A. Procédé de fabrication d'un 1,2-epoxyde
CN102361861B (zh) * 2009-03-25 2015-09-02 昭和电工株式会社 环氧化合物的制造方法
WO2011010614A1 (fr) 2009-07-24 2011-01-27 荒川化学工業株式会社 Procédé pour la fabrication d'un composé époxyde et procédé pour l'époxydation d'une double liaison carbone-carbone
EP2343288A1 (fr) 2009-11-27 2011-07-13 Momentive Specialty Chemicals Research Belgium S.A. Processus de fabrication d'oxyde de propylène
EP2354131A1 (fr) 2010-02-02 2011-08-10 Momentive Specialty Chemicals Research Belgium Procédé de fabrication de 1,2-époxyde et dispositif pour effectuer ce procédé
CN102311408B (zh) * 2010-06-30 2015-06-03 山东瀛洋香精香料有限公司 废水零排放工艺制备环氧苯乙烷的方法
CN104119352B (zh) * 2013-04-26 2016-08-17 中国科学院大连化学物理研究所 一种烯烃的不对称环氧化方法
JP6609902B2 (ja) * 2013-10-02 2019-11-27 三菱ケミカル株式会社 エポキシ化合物の製造方法
CN104119300B (zh) * 2014-07-29 2016-07-06 浙江大学 一种α-蒎烯环氧化制备2,3-环氧蒎烷的方法
WO2016189548A1 (fr) * 2015-05-27 2016-12-01 Council Of Scientific & Industrial Research Procédé permettant la préparation d'époxydes d'aryloléfines cycliques et acycliques à l'aide de promoteurs organiques recyclables
CN106565634A (zh) * 2016-10-31 2017-04-19 广州百花香料股份有限公司 一种α‑蒎烯环氧化制备2,3‑环氧蒎烷的生产方法
MY193413A (en) * 2018-07-30 2022-10-12 Kao Corp Method for producing epoxyalkane and solid oxidation catalyst
KR102609700B1 (ko) * 2019-10-29 2023-12-06 한화솔루션 주식회사 사이클로도데카논 및 이의 제조방법
KR102609694B1 (ko) * 2019-10-29 2023-12-06 한화솔루션 주식회사 사이클로도데카논 및 이의 제조방법
CN112341407A (zh) * 2020-10-23 2021-02-09 如皋市丹凤纺织有限公司 一种纱线浸渍助剂合成方法
CN114956955A (zh) * 2021-02-25 2022-08-30 大加香料技术(天津)有限公司 一种β-苯乙醇的合成方法
CN114733511B (zh) * 2022-05-23 2023-04-14 扬州大学 V2O5/FeVO4催化剂在环辛烯环氧化反应中的应用

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Also Published As

Publication number Publication date
KR101131207B1 (ko) 2012-03-28
KR20070020016A (ko) 2007-02-16
CN1926124A (zh) 2007-03-07
JP2008500967A (ja) 2008-01-17
CN1926124B (zh) 2011-03-23
JP4733109B2 (ja) 2011-07-27
WO2005095370A1 (fr) 2005-10-13

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