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Process for the Preparation of Cyclic Carboxylic Anhydrides

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Process for the Preparation of Cyclic Carboxylic Anhydrides Europaisches Patentamt J European Patent Office CD Publication number: 0 293 053 Office europeen des brevets A2 EUROPEAN PATENT APPLICATION © Application number: 88201056.4 int. ci.<: C07C 51/56 , C07C 55/02 @ Date of filing: 25.05.88 © Priority: 27.05.87 GB 8712455 © Applicant: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V. ® Date of publication of application: Carel van Bylandtlaan 30 30.11.88 Bulletin 88/48 NL-2596 HR Den Haag(NL) © Designated Contracting States: © Inventor: Drent, Eit BE DE FR GB IT NL Badhuisweg 3 NL-1031 CM Amsterdam(NL) © Representative: Aalbers, Onno et al P.O. Box 302 NL-2501 CH The Hague(NL) © Process for the preparation of cyclic carboxylic anhydrides. © Process for the preparation of cyclic anhydrides of alkanedioic acids having 4 or 5 carbon atoms in the ring, by reacting an alkenoic acid with CO in the presence of (a) a palladium compound, (b) a phosphine, arsine and/or stibine, and (c) a protonic acid having a pKa < 2. CM < CO ID CO CM Q. Ill Xerox Copy Centre 0 293 053 PROCESS FOR THE PREPARATION OF CYCLIC CARBOXYL1C ANHYDRIDES The invention relates to a process for the preparation of cyclic anhydrides of optionally substituted alkanedioic acids having 4 or 5 carbon atoms in the ring or of a mixture of such cyclic anhydrides. Such cyclic anhydrides may be prepared as described in Bull. Soc. Chim. Fr. 1975, (9-10, Pt. 2), 2189- 2194, by acid hydrolysis and decarboxylation of diethyl beta-alkyl-alpha-cyanosuccinate, the aikyl group 5 being an ethyl or a propyl group, to give monosubstituted acids, HO2CCH = CH2CH(R)CO2H, Ft being an ethyl or a propyl group, which were transformed to the anhydrides by heating. This known process for the preparation of cyclic anhydrides requires a starting material which is difficultly accessible. It is an object of the present invention to prepare the cyclic anhydrides mentioned hereinbefore in a simple manner from simple starting compounds and with high selectivity. to Accordingly, the invention provides a process for the preparation of cyclic anhydrides of optionally substituted alkanedioic acids having 4 or 5 carbon atoms in the ring or of a mixture of such cyclic anhydrides which process comprises reacting an optionally substituted alkenoic acid with carbon monoxide in the presence of a catalytic system obtainable by combining the following components:- component (a) - a palladium compound, 75 component (b) - a phosphine, arsine and/or stibine, and component (c) - a protonic acid having a pKa, measured at 25 'C in aqueous solution, of less than 2. The process according to the present invention is carried out in the liquid phase in which the palladium compound may be heterogeneous but is preferably homogeneous. Suitable homogeneous palladium compounds are the salts of palladium(ll) with, for instance, nitric acid, sulphuric acid, or, which is preferred, 20 alkanoic acids having not more than 12 carbon atoms per molecule. A palladium compound used by preference is palladium(ll) acetate. Other examples of palladium(ll) compounds are palladium(ll) formate and palladium(ll) propanoate. Salts of hydrohalogenic acids may also be used. Moreover, palladium complexes may be used, for instance palladium acetylacetonate, tetrakistriphenylphosphinepalladium, bis-tri-o-tolyl- phoshinepalladium acetate or bis-triphenylphosphinepalladium sulphate. A mixture of palladium compounds 25 may be used as component (a). It has, surprisingly, been found that the process according to the present invention allows the preparation of cyclic anhydrides of optionally substituted alkanedioic acids having four carbon atoms in the ring with an extremely high selectivity. The selectivity to a certain compound, expressed in a percentage, is defined herein as 100 x p:q in which "p" is the amount of starting compound that has been converted into 30 that certain compound and "q" is the total amount of starting compound that has been converted. Therefore, according to a preferred embodiment of the present invention compound (b) is a chelating ligand comprising an organic compound containing as coordinating atoms at least two atoms of phosphorus, arsenic or antimony which are connected through a divalent organic bridging group having at least two carbon atoms in the bridge. For example, by this preferred embodiment 3-pentenoic acid can be converted 35 quantitatively into ethylsuccinic anhydride. The two or more coordinating atoms may be the same or different, for example two arsenic atoms, a phosphorus or an arsenic atom, or an arsenic and an antimony atom. The chelating ligand preferably has the general formula I R1 R3 R5 40 - P - - P - (I) RZ R in which R\ R2, R4 and R5 represent identical or different optionally substituted hydrocarbon groups and R3 represents a chain consisting of two to six optionally substituted methylene groups. Any substituents 45 present in the chelating ligand preferably do not cause steric hindrance to the formation of complex compounds with the palladium(ll) compound. Hydrocarbon groups R1, R2, R* and R5 will as a rule contain 2 to 18 carbon atoms, preferably 6 to 14 carbon atoms. Aryl groups are the most suitable, in particular the phenyl group. Preferred bridging groups -R3- are those having the formula --{@ CR6R7 -)- in which R6 and R7 are hydrogen atoms or optionally 50 „ substituted hydrocarbon groups preferably offering no steric hindrance and n is an integer of at least two, preferably not more than 5, and most preferably 2, 3 or 4. Substituents Rs and R7 are preferably hydrogen atoms. The bridging groups R3 may also make part of a cyclic structure, e.g. an aromatic or cycloaliphatic group, the carbon to carbon bond or bonds in the bridge may be saturated or unsaturated and in the bridge or in the cyclic or non-cyclic groups attached to the bridge one or more hetero atoms, e.g. sulphur, oxygen, 0 293 053 iron or nitrogen atoms, may replace carbon atoms, other than the two carbon atoms which must be present in the bridge linking both phosphorus atoms. Examples of suitable chelating ligands are 1,3-di(diphenylphosphino)propane, 5 1 ,4-di(diphenylphosphino)butane, 2,3-dimethyl-1,4-di(diphenylphosphino)butane, 1,5-di(methylphenylphosphino)pentane, 1,4-di(dicyclohexylphosphino)butane, 1,5-di(dinaphthylphosphino)pentane, 10 1 ,3-di(di-p-tolylphosphino)propane, 1,4-di(di-p-methoxyphenylphosphino)butane, 1,2-di(diphenylphosphino)ethene, 2,3-di(diphenylphosphino)-2-butene, 1,3-di(diphenylphosphino)-2-oxopropane, 75 2-methyl-2-(methyldiphenylphosphino)-1,3-di(diphenylphosphino)propane, o,o -di(diphenylphosphino)biphenyl, 1,2-di(diphenylphosphino)benzene, 2,3-di(diphenylphosphino)naphthalene, 1,2-di(diphenylphosphino)cyclohexane, 20 2,2-dimethyl-4,5-di(diphenylphosphino)dioxolane and ^V_Fe-_/TA 25 / / PIC6H5»2 P(C6H5»2 30 Very good results have been obtained with 1,4-di(diph3nylphosphino)butane. A mixture of chelating ligands of the general formula I may be used. Furthermore, it has surprisingly been found that the process according to the present invention allows the preparation of a mixture of a cyclic anhydride of an optionally substituted alkanedioic acid having 4 35 carbon atoms in the ring and a cyclic anhydride of an optionally substituted alkanedioic acid having 5 carbon atoms in the ring with an extremely high selectivity to the total of the two anhydrides. Therefore, according to a preferred embodiment of the present invention compound (b) has the general formula II 40 R7 R64-R8 (ID in which Rs, R7 and R8 each individually represent an optionally substituted aryl group. For example, by 45 this preferred embodiment 3-pentenoic acid can be converted quantitatively into a mixture of ethylsuccinic anhydride and 2-methylglutaric anhydride. The substituted or unsubstituted aryl groups Rs, R7 and R8 of the phosphine of the general formula II preferably contain not more than 18, in particular in the range of from 6 to 14 carbon atoms. Examples of suitable Rs, R7 and R8 groups are the naphthyl group and in particular, the phenyl group. Suitable so substituents are halogen atoms and alkyl, aryl, alkoxy, carboxy, carbalkoxy, acyl, trihalogenmethyl, cyano, dialkylamino, sulphonylalkyl and alkanoyloxy groups. Examples of suitable phosphines are tri-p-tolylphosphine, tri(p-chlorophenyl)phosphine, tri-p-methox- yphenylphosphine, o-di phenylphosphinobenzoic acid and in particular triphenylphosphine. A mixture of phosphines of the general formula II may be used. 55 A mixture of chelating ligands of the general formula I and phosphines of the general formula II may be used as component (b). In this case cyclic anhydrides of optionally substituted alkanedioic acids having four carbon atoms in the ring are usually formed with an extremely high selectivity. The protonic acid having a pKa of less than 2 preferably has an anion which is non-coordinating, by 0 293 053 the anion of the which is meant that little or no covalent interaction takes place between the palladium and protonic acid. A preferred group of acids has the general formula III 5 CX 0 r9_^_oh (III) R3 an in which X represents a sulphur or a chlorine atom and, if X represents a chlorine atom, represents 70 OH an optionally substituted oxygen atom and, if X represents a sulphur atom, R9 represents an group or hydrocarbon group. of When the hereinbefore stated acids are used in the process according to the invention, the anions the acids can be considered to be non-coordinating. In the acids having the general formula III, the optionally substituted hydrocarbon group represented by 7515 carbon atoms. The R3 is preferably an alkyl, aryl, aralkyl or alkaryi group having 1-30, in particular 1-14, in fluorine atoms. hydrocarbon group may, for example, be substituted with halogen atoms, particular and Preferred acids of the general formula III are perchloric acid, sulphuric acid, p-toluenesulphonic acid acid is 2- trifluoromethanesulphonic acid.
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