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Ep 2531496 B1 (19) TZZ ¥__T (11) EP 2 531 496 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07D 301/12 (2006.01) C07D 303/16 (2006.01) 15.03.2017 Bulletin 2017/11 (86) International application number: (21) Application number: 11701942.2 PCT/EP2011/000322 (22) Date of filing: 26.01.2011 (87) International publication number: WO 2011/095294 (11.08.2011 Gazette 2011/32) (54) MANUFACTURE OF AN EPOXYETHYL CARBOXYLATE OR GLYCIDYL CARBOXYLATE HERSTELLUNG VON EPOXYDETHYLCARBOXYLAT ODER GLYCIDYLCARBOXYLAT FABRICATION DE CARBOXYLATE ÉPOXYÉHTYL OU CARBOXYLATE GLYCIDYLIQUE (84) Designated Contracting States: (56) References cited: AL AT BE BG CH CY CZ DE DK EE ES FI FR GB EP-A1- 0 618 202 EP-A1- 2 149 569 GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO WO-A1-2005/089549 US-A- 4 423 071 PL PT RO RS SE SI SK SM TR US-A- 6 136 991 US-A1- 2003 069 439 US-A1- 2006 100 348 (30) Priority: 02.02.2010 EP 10001034 • DE VOS D E ET AL: "Epoxidation of Terminal or (43) Date of publication of application: Electron-deficient Olefins with H2O2, catalysed 12.12.2012 Bulletin 2012/50 by Mn-trimethyltriazacyclonane Complexes in the Presence of an Oxalate Buffer", (73) Proprietor: Hexion Research Belgium SA TETRAHEDRON LETTERS, ELSEVIER, 1348 Ottignies Louvain-la-Neuve (BE) AMSTERDAM, NL LNKD- DOI:10.1016/S0040-4039(98)00205-6, vol. 39, no. (72) Inventors: 20, 14 May 1998 (1998-05-14), pages 3221-3224, • MUPPA, Prasad XP004116236, ISSN: 0040-4039 NL-3196 KK Vondelingenplaat Rt (NL) • BRACE N. O. ET AL: "Hydrophobic Compounds • POSTMA, Ron and Polymers from Long Chain NL-3196 KK Vondelingenplaat Rt (NL) Alkanamide-Formaldehyde Condensation • SCHOOLDERMAN, Caspar Reactions", JOURNAL OF ORGANIC NL-3196 KK Vondelingenplaat Rt (NL) CHEMISTRY, vol. 26, 1 December 1961 • RENS, Sandra (1961-12-01), pages 5176-5180, XP002586994, NL-3196 KK Vondelingenplaat Rt (NL) • STOITSAS, Kostas NL-3196 KK Vondelingenplaat Rt (NL) Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 531 496 B1 Printed by Jouve, 75001 PARIS (FR) EP 2 531 496 B1 Description Field of invention 5 [0001] The invention relates to a process for the manufacture of an epoxyethyl carboxylate or glycidyl carboxylate by reacting a vinyl carboxylate or an allyl carboxylate with an oxidant in the presence of a manganese complex. Background of invention 10 [0002] Glycidyl esters are an important starting material in the chemical industry. The glycidyl esters are typically prepared by reaction of epichlorohydrin with a carboxylic acid in the presence of catalyst and subsequent dehydrochlo- rination of the resulting mixture of chlorohydrin esters followed by their separation. In particular the glycidyl esters of branched carboxylic acids and epoxy specialties are of commercial importance, which find use in the production of high- grade alkyd resins, polyester resins, acrylic resins, and a variety of other resins, and also as reactive diluent. Of particula r 15 interest are the glycidyl esters commercialised under the CARDURA™ trademark, which have been used for decades as a building block for automotive OEM, Refinish and CED coatings. The Glycidyl Ester of Versatic™ acid exhibits UV stability, acid etch resistance and a unique ability to create high solids low viscosity polymers with good substrate wetting. [0003] Of similar interest is the 1,2-epoxyethyl carboxylate, for instance the product of the epoxidation of vinyl pivalate and in particular the product of the epoxidation of a vinyl ester of a branched carboxylic acid. Such esters are commercially 20 available under the VEOVA™ trademark. [0004] Epoxidation of vinyl esters or allyl esters is uncommon. According to the literature it is possible to epoxidize vinyl acetate by using a Ti-MWW/H2O2 catalytic system ("Epoxidation of Various Functionalized Olefins by a Ti-MWW/ H2O2 Catalytic System", by LI Ningnin et al in Chin J Catal, 2008, 29(2): 102-104). From this reference it is known that the epoxidation of a C=C bond is more difficult when the C=C bond is connected to groups having a high electron drawing 25 group. The epoxidation of vinyl esters is even more difficult than the epoxidation of allyl esters. This is because the C=C bond in the vinyl group is conjugated with the C=O bond or adjacent to the C-O bond, which makes it electronically more deficient than the C=O bond in the allyl group. The conversion and product selectivity of, for example, allyl acetate epoxidation were higher than that of vinyl acetate epoxidation. [0005] In "Synthesis of some epoxy vinyl monomers by epoxidation with peracetic acid" by F.C. Frostick et al, JACS, 30 81 (1958) 3350, the epoxidation of vinylpent-4-enoate is described, resulting in the production of vinyl 4,5-epoxypen- tanoate. The vinyl group is not epoxidized. In the same report reaction constants are given for reaction esters (vinyl acetate, ethyl acrylate, allyl acetate, allyl ether). As can be concluded from the reaction constants, epoxidation of esters is very slow (in some cases does not happen like vinyl acetate and ethyl acrylate). [0006] In EP0618202 various olefins such as 4-vinylbenzoic acid, styrylacetic acid, trans-3-hexenoic acid, trans-2- 35 hexenoic acid and allyl alcohol are epoxidized by contact with a source of oxygen and a Mn complex, such as a binuclear manganese complex, in which the Mn is co-ordinated to an N-containing ligand such that there is a ratio of Mn to co- ordinated N atoms of 1:3. Suitable olefins include compounds with from 2 to 50 carbon atoms, such as those having from 3 to 20 carbon atoms. They may be selected from mono- or multi-substituted and unsubstituted, branched or unbranched alkenes and arylalkenes. Substitution of the alkenes may be in the form of hetero atom functional groups 40 including those of halo, cyano, carboxylate, sulphate, phosphate, amino, hydroxyl, nitro, alkoxy, acyloxy and combinations thereof. When the epoxidation process is conducted in an aqueous media, best results are obtained on olefins with water-soluble groups such as those with carboxylate and hydroxyl units, e.g. vinylbenzoic acid, styrylacetic acid and hexenoic acid. This reference does not disclose the epoxidation of vinyl carboxylates or allyl carboxylates [0007] EP 2149569 discloses a process for the preparation of glycidyl acetate where the terminal olefin is selected 45 from esters of alkenoic acids or allyl esters of alkanoic acids. [0008] 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, vol. 39, no. 20, 14 May 1998, pages 3221-3224 sets forth the preparation process of glycidyl acetate starting from allyl acetate. [0009] The inventors set out to find an alternative route to glycidyl esters of carboxylic acids that does not rely on 50 epichlorohydrin. Such an alternative route has been found. Moreover, this new route also opens the possibility of preparing epoxyethyl esters of carboxylic acids which will find use in the same applications where the glycidyl esters are used. [0010] The present invention provides an attractive route to such products. Disclosure of the Invention 55 [0011] Accordingly, the invention provides a process for the manufacture of an epoxyethyl carboxylate or glycidyl carboxylate, comprising: 2 EP 2 531 496 B1 reacting a vinyl carboxylate or an allyl carboxylate using an oxidant and a water-soluble manganese complex in an aqueous reaction medium, wherein the water-soluble manganese complex is an oxidation catalyst, characterized in that the water-soluble manganese complex is a binuclear species of the general formula (II): 5 n’ [LMn(m-X)3MnL]Y (II) , wherein Mn is a manganese; L or each L independently is a polydentate ligand wherein each polydentate ligand 10 is independently selected from acyclic compounds containing at least 7 atoms in the backbone or cyclic com- pounds containing at least 9 atoms in the ring, wherein each polydentate ligand having 3 nitrogen atoms with the nitrogen atoms separated by at least two carbon atoms.; and each m-X is independently a bridging coordi- - - - - - - - - nating species, selected from the group consisting of: R"O , Cl , Br , I , F , NCS , N3 , I3 , NH3, NR"3, R"COO , - - - 2- 2- - - - - 2- R"SO3 , RSO4 , OH , O , O2 HOO , H2O, SH , CN , OCN , and S4 and combinations thereof, wherein R" is 15 a C1-C20 radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl and combinations thereof, and Y is a non-coordinating counter ion selected from CH 3COO or PF 6 , n’ is 1 or 2, and wherein the epoxidation is carried out at a pH in the range of from 1.0 to 7.0 [0012] The epoxidation products of the vinyl esters of highly branched acids are believed to be novel. Accordingly, 20 this invention also relates to epoxyethyl esters of neoacids (wherein R is a tertiary alkyl group) having from 5 to 30 carbon atoms in the acid moiety. Mode(s) for carrying out the Invention 25 [0013] As used in the current specification, the expressions epoxidation and oxidation refer to the same reaction; the conversion of the carbon-carbon double bond of the vinyl group or the allyl group into an oxirane ring.
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