WO2013113578A1 - Procédé de production d'esters d'acides époxy-carboxyliques - Google Patents

Procédé de production d'esters d'acides époxy-carboxyliques Download PDF

Info

Publication number
WO2013113578A1
WO2013113578A1 PCT/EP2013/051034 EP2013051034W WO2013113578A1 WO 2013113578 A1 WO2013113578 A1 WO 2013113578A1 EP 2013051034 W EP2013051034 W EP 2013051034W WO 2013113578 A1 WO2013113578 A1 WO 2013113578A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
capillaries
reaction
tubular reactor
manganese
Prior art date
Application number
PCT/EP2013/051034
Other languages
German (de)
English (en)
Inventor
Joaquim Henrique Teles
Rainer Klopsch
Bianca Seelig
Original Assignee
Basf Se
Basf Schweiz Ag
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 Basf Se, Basf Schweiz Ag filed Critical Basf Se
Priority to KR1020147018629A priority Critical patent/KR20140117386A/ko
Priority to JP2014555144A priority patent/JP2015529628A/ja
Priority to EP13701049.2A priority patent/EP2809663A1/fr
Priority to CN201380007204.1A priority patent/CN104093710A/zh
Publication of WO2013113578A1 publication Critical patent/WO2013113578A1/fr

Links

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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals

Definitions

  • the present invention relates to a process for the preparation of epoxides of the formula I.
  • R is an organic group having 1 to 10 carbon atoms, by reacting compounds of formula II with an oxidizing agent, which is characterized in that the preparation is carried out continuously in a tubular reactor.
  • Epoxides are of great importance for a wide variety of technical applications and, in particular, as starting materials for further chemical syntheses.
  • Epoxides of the formula I are z. B. Ausgansstoffe for the preparation of carbonates, as described in the unpublished patent applications PCT / EP201 1/058945 and PCT / EP201 1/069626.
  • EP-A 2 354 131 mentioned. However, EP-A 2 354 131 does not relate to the epoxidation of acrylates.
  • the object of the present invention was a simple and effective process for the preparation of epoxides from acrylates;
  • the epoxides should be obtained in particular with the highest possible yield and selectivity.
  • R is an organic group having 1 to 10 carbon atoms.
  • the organic group may also contain heteroatoms, for example oxygen and nitrogen. The latter in particular as part of a hydroxyl, ether, amino or nitro group.
  • R contains no heteroatoms and therefore represents a hydrocarbon group.
  • the hydrocarbon group may be an aromatic or aliphatic hydrocarbon group.
  • R is a C1 to C10 alkyl group.
  • the alkyl group may be linear or branched.
  • R particularly preferably represents a C 1 - to C 4 -alkyl group, such as a methyl, ethyl, n-propyl, isopropyl, n-butyl or part. Butyl group.
  • R is a methyl group.
  • the starting compound of the formula II is then a C 1 - to C 10 - or a C 1 - to C 4 -alkyl acrylate and very particularly preferably methyl acrylate.
  • the compounds of the formula I are reacted with an oxidizing agent.
  • the oxidizing agent are conventional oxidizing agents, eg. As peroxides or peracids, into consideration.
  • Preferred oxidizing agent is hydrogen peroxide (H2O2).
  • Hydrogen peroxide is preferably used in the form of an aqueous solution.
  • the concentration of hydrogen peroxide in water is preferably 10 to 70 wt.%, In particular 20 to 60 wt.%, Based on the solution (ie total weight of hydrogen peroxide and water).
  • the oxidizing agent preferably hydrogen peroxide, is preferably used in molar excess so that the starting compound of the formula I is reacted as completely as possible; the oxidizing agent may, for. B. in amounts of 1, 1 to 2 equivalents, in particular from 1, 2 to 1, 7 equivalents, based on 1 equivalent of the starting compound of formula II, can be used.
  • the reaction is carried out in the presence of a manganese complex as a catalyst.
  • Suitable manganese complexes are those as described in Albrecht Berkessel et al, Tetrahedron Letters 40 (1999), 7965-7968 and Dirk E.de Vos et al, Tetrahedron Letters 39 (1998), 3221-3224. Preference is given to manganese / nitrogen complexes, preferably those in which the manganese in its respective oxidation state is coordinated to three nitrogen atoms.
  • the reaction mixture the starting compounds of the manganese / nitrogen complex, which are a manganese salt and a suitable complexing nitrogen compound added.
  • the catalytic effect then occurs with the in situ formation of the manganese / nitrogen complex.
  • the manganese / nitrogen complex ultimately catalyzes the decomposition of the hydrogen peroxide, which is accompanied by a change in the manganese cation between the oxidation states III to V.
  • Suitable manganese salts are, in particular, salts of divalent manganese, such as MnSO 4 .
  • a well-complexed nitrogen compound is e.g. 1, 4,7-trimethyl-1, 4,7-triazacyclononane (abbreviated TMTACN).
  • the manganese / nitrogen complex or the manganese salt and the nitrogen compound respectively in amounts of 0.005 to 0.2 mol, more preferably from 0.01 to 0.1 mol and most preferably from 0.02 to 0.08 mol per 100 mol of the starting compound of formula II.
  • a cocatalyst is preferably used.
  • Suitable cocatalysts are, in particular, a reducing agent, such as ascorbic acid, squaric acid, oxalic acid or an oxalate, eg. For example, sodium oxalate.
  • a reducing agent such as ascorbic acid, squaric acid, oxalic acid or an oxalate, eg.
  • sodium oxalate oxalic acid or an oxalate.
  • Particularly preferred is an oxalic acid / oxalate system; this acts as a buffer.
  • the amount of cocatalyst may, for. B. 0.1 to 20 mol, in particular 0.5 to 10 mol and more preferably 1 to 5 mol per 100 mol of the starting compound II.
  • the epoxides of the formula II are prepared continuously in a tube reactor.
  • the starting materials are fed continuously to the tubular reactor and the resulting product mixture is continuously removed.
  • the above starting materials can be supplied separately; but it can also be mixed any of the above starting materials and fed to the tubular reactor as a mixture.
  • two mixtures are prepared in advance,
  • an aqueous solution containing the water-soluble starting materials preferably hydrogen peroxide and oxalic acid / oxalate, and
  • an organic solution which comprises the compound of the formula II and starting compounds soluble therein; it is preferably a solution of the manganese-nitrogen complex or its starting compounds in the acrylic compound of the
  • the reaction in the tubular reactor is exothermic and occurs immediately.
  • the crude reactor is cooled, so that the reaction is preferably carried out at a temperature in the tubular reactor from 0 to 40 ° C, in particular 0 to 30 ° C.
  • the reaction can be carried out at atmospheric pressure, reduced pressure or elevated pressure.
  • a slight overpressure of an inert gas, in particular nitrogen whereby a bubble-free distribution, mixing and transport of the reaction medium in the tubular reactor is favored.
  • the overpressure can z. B. 1 to 10 bar.
  • the term tubular reactor should be understood here as the entire reactor unit; this can consist of a single tube or several tubes connected in parallel.
  • the tubes preferably have only a small inner diameter and are therefore also called capillaries.
  • the tube reactor consists of one or more parallel connected, perfused by the reaction mixture capillaries, the capillaries have an inner diameter less than 5 millimeters, in particular less than 3 millimeters; In particular, an inner diameter of less than 2 or less than 1 millimeter is also suitable.
  • the inner diameter of the capillaries is generally at least 0.1 millimeter.
  • Very particularly preferred internal diameters of the capillaries are in the range from 0.1 to 5 millimeters, in particular from 0.2 to 4 millimeters, very particularly preferably from 0.5 to 3 millimeters.
  • Inner diameter of the capillaries is understood here as the largest diameter along the cross-sectional area; for a circular or semicircular cross-section of the capillaries, this is twice the radius.
  • the length of the capillaries is preferably at least 5, in particular at least 10 meters.
  • Very suitable tubular reactors have e.g. one or more capillaries with a length of 10 to 150 meters, in particular of 20 to 130 meters and in a particularly preferred embodiment of 30 to 100 meters.
  • the tubular reactor consists of at least two parallel capillaries, z. B. from 2 to 5 parallel capillaries, in particular it consists of two parallel capillaries.
  • the residence time of the reaction mixture in the tubular reactor or the capillaries is preferably from 5 to 200 minutes, more preferably from 10 to 100 minutes, particularly preferably from 20 to 80 minutes.
  • a single-phase or two-phase reaction product is obtained after passing through the tubular reactor. If and insofar as the obtained epoxide of the formula I is soluble in water, an aqueous phase containing the epoxide is obtained. If the epoxide obtained is not soluble in water or more epoxide is obtained than is soluble in water, it precipitates next to the aqueous phase, which consists essentially of the epoxide.
  • the organic phase (epoxide) can be separated in a simple manner; From the aqueous phase, the epoxide obtained can be isolated by known methods, for example by extraction.
  • EPSME Methyl Epoxypropionate
  • R is a methyl radical
  • TMTACN 1, 4,7-trimethyl-1, 4,7-triazacyclononane. The preparation was carried out continuously as described below
  • feed containers were filled with a solution of methyl acrylate / TMTACN / Mn (II) acetate (reservoir B1) or a solution of H 2 O 2 / Na oxalate / oxalic acid (reservoir B2) and for better promotion and prevention of gas bubbles in the pump heads superimposed with 5 bar of nitrogen.
  • the mass flows 1 (methyl acrylate / TMTACN / Mn (II) acetate) and 2 (hydrogen peroxide + sodium oxalate + oxalic acid) were conveyed by means of Kontron or Bischoff pumps (controlled by the balance value) in the reactor.
  • the reactor consisted of two parallel semicircular microchannels with a radius of 1 .2 mm and a total volume of 200 ml.
  • the mass flows were mixed immediately before the reactor, passed through the reactor and depressurized (20 bar) into the discharge tank. To avoid post-reaction, excess hydrogen peroxide was decomposed by saturated sodium sulfite solution in the discharge vessel.
  • Example 1 20 wt. % aqueous H 2 O 2 solution
  • TMTACN 1.0 g TMTACN / kg reaction product (EPSME)
  • Example 2 30 wt. % aqueous H 2 O 2 solution
  • Example 3 50 wt. % aqueous H 2 O 2 solution
  • the solubility of EPSME in water is 43 g / 100 g H20 at 20 ° C.
  • the density of EPSME is 1.16 g / ml - i. from a yield of about 40% (at 50% H 2 O 2), the reaction effluent is biphasic - an upper aqueous phase and a lower phase of EPSME.
  • the lower phase was separated and extracted in the upper phase dissolved EPSME.
  • the solvent was removed under reduced pressure and the ESPME crude product at a transition temperature

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

La présente invention concerne un procédé de production d'époxydes de formule (I) dans laquelle R représente un groupe organique comprenant de 1 à 10 atomes de C, par une réaction des composés de formule (II) avec un oxydant, caractérisé en ce que la production se déroule en continu dans un réacteur tubulaire.
PCT/EP2013/051034 2012-01-31 2013-01-21 Procédé de production d'esters d'acides époxy-carboxyliques WO2013113578A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020147018629A KR20140117386A (ko) 2012-01-31 2013-01-21 에폭시-카르복실산 에스테르의 제조 방법
JP2014555144A JP2015529628A (ja) 2012-01-31 2013-01-21 エポキシドの製造方法
EP13701049.2A EP2809663A1 (fr) 2012-01-31 2013-01-21 Procédé de production d'esters d'acides époxy-carboxyliques
CN201380007204.1A CN104093710A (zh) 2012-01-31 2013-01-21 制备环氧基羧酸酯的方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP12153206 2012-01-31
EP12153206.3 2012-01-31

Publications (1)

Publication Number Publication Date
WO2013113578A1 true WO2013113578A1 (fr) 2013-08-08

Family

ID=47603691

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2013/051034 WO2013113578A1 (fr) 2012-01-31 2013-01-21 Procédé de production d'esters d'acides époxy-carboxyliques

Country Status (5)

Country Link
EP (1) EP2809663A1 (fr)
JP (1) JP2015529628A (fr)
KR (1) KR20140117386A (fr)
CN (1) CN104093710A (fr)
WO (1) WO2013113578A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8940940B2 (en) 2012-06-13 2015-01-27 Basf Se Process for preparing macrocyclic ketones
US10087158B2 (en) * 2015-02-17 2018-10-02 Evonik Degussa Gmbh Method for the epoxidation of an olefin with hydrogen peroxide
US10196370B2 (en) 2015-02-17 2019-02-05 Evonik Degussa Gmbh Method for the epoxidation of an olefin with hydrogen peroxide

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5329024A (en) 1993-03-30 1994-07-12 National Starch And Chemical Investment Holding Corporation Epoxidation of olefins via certain manganese complexes
EP1489074A1 (fr) * 2003-06-18 2004-12-22 Degussa AG Procédé pour l'epoxydation de propène
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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10020632A1 (de) * 2000-04-27 2001-10-31 Merck Patent Gmbh Verfahren zur Expodierung von Olefinen
EP2354130A1 (fr) * 2010-02-02 2011-08-10 Momentive Specialty Chemicals Research Belgium Fabrication de carboxylate époxyéhtyl ou carboxylate glycidylique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5329024A (en) 1993-03-30 1994-07-12 National Starch And Chemical Investment Holding Corporation Epoxidation of olefins via certain manganese complexes
EP1489074A1 (fr) * 2003-06-18 2004-12-22 Degussa AG Procédé pour l'epoxydation de propène
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

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
ALBRECHT BERKESSEL ET AL., TETRAHEDRON LETTERS, vol. 40, 1999, pages 7965 - 7968
DE VOS D E ET AL: "Epoxidation of Terminal or Electron-deficient Olefins with H2O2, catalysed by Mn-trimethyltriazacyclonane Complexes in the Presence of an Oxalate Buffer", TETRAHEDRON LETTERS, ELSEVIER, AMSTERDAM, NL, vol. 39, no. 20, 14 May 1998 (1998-05-14), pages 3221 - 3224, XP004116236, ISSN: 0040-4039, DOI: 10.1016/S0040-4039(98)00205-6 *
DIRK E.DE VOS ET AL., TETRAHEDRON LETTERS, vol. 39, 1998, pages 3221 - 3224
MCPAKE C B ET AL: "Epoxidation of alkenes using HOF.MeCN by a continuous flow process", TETRAHEDRON LETTERS, ELSEVIER, AMSTERDAM, NL, vol. 50, no. 15, 15 April 2009 (2009-04-15), pages 1674 - 1676, XP025989811, ISSN: 0040-4039, [retrieved on 20090225], DOI: 10.1016/J.TETLET.2008.12.073 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8940940B2 (en) 2012-06-13 2015-01-27 Basf Se Process for preparing macrocyclic ketones
US10087158B2 (en) * 2015-02-17 2018-10-02 Evonik Degussa Gmbh Method for the epoxidation of an olefin with hydrogen peroxide
US10196370B2 (en) 2015-02-17 2019-02-05 Evonik Degussa Gmbh Method for the epoxidation of an olefin with hydrogen peroxide

Also Published As

Publication number Publication date
EP2809663A1 (fr) 2014-12-10
KR20140117386A (ko) 2014-10-07
JP2015529628A (ja) 2015-10-08
CN104093710A (zh) 2014-10-08

Similar Documents

Publication Publication Date Title
EP1076654B1 (fr) Procede de preparation continue de 1,3-dioxolane-2-ones
EP0654461B1 (fr) Procédé de préparation de carbonates de diaryle
DE19619949A1 (de) Verfahren zur Herstellung von Diarylcarbonaten
DE3205464A1 (de) Verfahren zur herstellung von n-octanol
DE60001881T3 (de) Verfahren zur Herstellung von Olefinoxiden
WO2008125241A1 (fr) Procédé de préparation d'acides alkylpolyglycolcarboxyliques et d'acides polyglycoldicarboxyliques par oxydation directe
EP2809663A1 (fr) Procédé de production d'esters d'acides époxy-carboxyliques
DE2632158C3 (de) Verfahren zur Herstellung von vicinalen Hydroxycarboxylaten und Dicarboxylaten
DE1793217A1 (de) Verfahren zum Epoxydieren von olefinischen Verbindungen
DE60013049T2 (de) Verfahren zur Herstellung von Olefinoxiden
DE3602254A1 (de) Verfahren zur herstellung von oxiranylcarbonsaeureestern
EP0700892B1 (fr) Procédé de préparation d'acides mono- ou dicarboxyliques à partir des aldéhydes, leurs acétals ou hemi-acétals, comme aussi à partir de leurs mélanges
DE2949847C2 (fr)
EP0090977B2 (fr) Procédé de préparation d'esters de l'acide carbonique
DD151621A5 (de) Verfahren zur herstellung von sauerstoffhaltigen kohlenstoffverbindungen und olefinen aus synthesegas
WO2016184953A1 (fr) Oxydation de limonène
DE3602180C2 (fr)
EP0074009B1 (fr) Procédé pour la préparation du tétraméthyl oxiranne
DE2201456C3 (de) Verfahren zur Herstellung von Aldehyden und Diolen
DE1768854A1 (de) Verfahren zur Herstellung von organischen Hydroperoxyden
DE2225450C3 (de) Verfahren zur gleichzeitigen Herstellung von Propylenoxid und Essigsäure
DE2241155C3 (de) Verfahren zur Herstellung von einfach oxalkylierten a -Acetylenalkoholen
DE2241156C3 (de) Verfahren zur Herstellung von Hydroxyäthyläthern von a -Acetylenalkoholen
EP0291805B1 (fr) Procédé pour la fabrication de p-hydroxyméthylbenzaldéhyde
DE4418508A1 (de) Verfahren zur Herstellung von p-Alkoxybenzaldehyden

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13701049

Country of ref document: EP

Kind code of ref document: A1

REEP Request for entry into the european phase

Ref document number: 2013701049

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2013701049

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 20147018629

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2014555144

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE