Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
  • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/44—Adipic acid esters

Definitions

• the present invention relates to a process for the hydrogenation of a monoolefinically unsaturated compound which carries at least two functional groups, independently selected from the group consisting of nitrile group, carboxylic acid group, carboxylic acid ester group, carboxamide group, to a saturated compound which carries the same at least two functional groups , in the presence of a rhodium-containing compound which is homogeneous with respect to the reaction mixture as catalyst.
• adipic acid or its derivatives are important starting compounds for the production of technically important polymers, such as polyamide 6 or polamide 66.
• Such compounds can be obtained, for example, by adding two terminal olefins which carry the functional groups required for the preparation of the monoolefinically unsaturated compound containing at least two functional groups.
• hexadioic diester can be prepared by adding acrylic acid esters in the presence of appropriate catalyst systems, as described, for example, in J. Organomet. Chem. 1987, 320, C56, US 4,451,665, FR 2,524,341, US 4,889,949, Organometallics, 1986, 5, 1752, J. Mol. Catal. 1993, 85, 149, US 4,594,447, Angew. Chem. Int. Ed. Engl., 1988, 27. 185, US 3,013,066, US, 4,638,084, EP-A-475 386, JACS 1991, 113, 2777-2779, JACS 1994, 116, 8038-8060.
• monoolefinically unsaturated compounds which carry at least two functional groups, independently selected from the group consisting of nitrile group, carboxylic acid group, carboxylic acid ester group, carboxamide group.
• the object of the present invention was to provide a process which carries out the hydrogenation of a monoolefinically unsaturated compound which has at least two functional groups, independently of one another, selected from the group consisting of nitrile group, carboxylic acid group, carboxylic acid ester group, carboxylic acid amide group, to give a saturated compound which carries the same at least two functional groups, in a technically simple and economical manner.
• catalysts in the context of the present invention relate to the compounds which are used as catalysts;
• the structures of the species which are catalytically active under the respective reaction conditions can differ from this, but are also included in the term “catalyst” mentioned.
• a monoolefinically unsaturated compound which bears at least two functional groups, independently selected from the group consisting of nitrile group, carboxylic acid group, carboxylic acid ester group, carboxylic acid amide group, is hydrogenated.
• suitable monoolefinically unsaturated compounds which carry at least two functional groups, independently of one another selected from the group consisting of nitrile group, carboxylic acid group, carboxylic acid ester group, carboxamide group, are those which are obtainable by adding two terminal olefins which carry the functional groups required for the preparation of the monoolefinically unsaturated compound containing at least two functional groups.
• esters of aliphatic, aromatic or heteroaromatic alcohols are advantageous.
• Preferred aliphatic alcohols are C do-alkanols, in particular C 1 -C 4 -alkanols, such as methanol, ethanol, i-propanol, n-propanol, n-butanoi, i-butanol, s-butanol, t-butanol , particularly preferably methanol are used.
• the carboxamide groups can be N- or N, N-substituted, where the N, N substitution can be the same or different, preferably the same.
• Preferred substituents are aliphatic, aromatic or heteroaromatic substituents, in particular aliphatic substituents, particularly preferably CrC 4 alkyl radicals, such as methyl, ethyl, i-propyl, n-propyl, n-butyl, i-butyl, s-butyl, t -Butyl, particularly preferably methyl.
• acrylic acid or its ester can be used as the terminal olefin with a functional group.
• the production of acrylic acid for example by gas phase oxidation of propene or propane in the presence of heterogeneous catalysts, and the production of acrylic acid esters, for example by esterification of acrylic acid with the corresponding alcohols in the presence of homogeneous catalysts, such as p-toluenesulfonic acid, are known per se.
• Acrylic acid is usually added during storage or processing, one or more stabilizers which, for example, avoid or reduce the polymerization or decomposition of acrylic acid, such as p-methoxyphenol or 4-hydroxy-2,2,4,4-piperidine-N -oxide ("4-hydroxy-TEMPO").
• stabilizers such as p-methoxyphenol or 4-hydroxy-2,2,4,4-piperidine-N -oxide ("4-hydroxy-TEMPO").
• Such stabilizers can be partially or completely removed in the addition step before the use of acrylic acid or its esters.
• the stabilizer can be removed by methods known per se, such as distillation, extraction or crystallization. Such stabilizers can remain in the amount previously used in acrylic acid.
• dimerization an addition product is obtained in the addition, which in this case is usually referred to as dimerization. This alternative is usually preferred for economic reasons.
• the monoolefinically unsaturated compound which carries at least two functional groups, independently of one another selected from the group consisting of nitrile group, carboxylic acid group, carboxylic acid ester group, carboxamide group, is hexadedioic acid diester, in particular dimethylhexenedioate, to obtain diester of adipate, in particular dimethyl adipate. by hydrogenation.
• Adipic acid can be obtained from cleavage of the ester group from diester of adipic acid, in particular dimethyl adipate.
• known processes for the cleavage of esters come into consideration.
• the monoolefinically unsaturated compound which bears at least two functional groups, independently of one another selected from the group consisting of nitrile group, carboxylic acid group, carboxylic acid ester group, carboxamide group, butenonitrile to obtain adiponitrile by hydrogenation.
• the monoolefinically unsaturated compound which bears at least two functional groups, independently of one another selected from the group consisting of nitrile group, carboxylic acid group, carboxylic acid ester group, carboxylic acid amide group, 5-cyanopentenoate, in particular methyl 5-cyanopentate, while obtaining 5-cyano valeric acid esters, in particular methyl 5-cyanovaleric acid, by hydrogenation.
• the addition of two terminal olefins mentioned can be carried out by methods known per se, as described, for example, in J. Organomet. Chem. 1987, 320, C56, US 4,451,665, FR 2,524,341, US 4,889,949, Organometallics, 1986, 5, 1752, J. Mol. Catal. 1993, 85, 149, US 4,594,447, Angew. Chem. Int. Ed. Engl., 1988, 27. 185,
• the addition can advantageously be carried out in the presence of a compound which is homogeneous with respect to the reaction mixture and contains rhodium, ruthenium, palladium or nickel, preferably rhodium, as the catalyst.
• the addition, in particular dimerization can be carried out in the presence of the same rhodium-containing compound which is homogeneous with respect to the reaction mixture as the catalyst as the hydrogenation of the monoolefinically unsaturated compound obtained by the addition according to the process of the invention.
• the hydrogenation of the monoolefinically unsaturated compound obtained by the addition can be carried out in accordance with the process according to the invention without separating or depleting the homogeneous rhodium-containing compound used as catalyst in the addition, in particular dimerization, of the olefins mentioned.
• reaction product obtained in the addition reaction in particular dimerization reaction, can be transferred without working up the hydrogenation step in accordance with the present process.
• a reactor such as a stirred tank, a boiler cascade, such as a stirred tank cascade, or a flow tube or in a combination of one of these types of reactors with another reactor suitable for the hydrogenation.
• the hydrogenation according to the invention can preferably be carried out in the presence of a rhodium-containing compound of the formula [L 1 Rhl_ 2 L 3 R] + X ' which is homogeneous with respect to the reaction mixture, in which
• L 1 is an anionic pentahapto ligand, preferably pentamethylcyclopentadienyl;
• L 2 represents a neutral 2-electron donor;
• L 3 represents a neutral 2-electron donor;
• R is selected from the group consisting of H, CrC 0 alkyl,
• C 6 aryl and C 7 -C ⁇ 0 0 -C ⁇ aralkyl ligands X "for a non-coordinating anion is preferably made for such a selected from the group consisting of BF 4 ', B (perfluorophenyl)", B (3,5-bis (trifluoromethyl) - phenyl) 4 ⁇ AI (OR F ) " where R F stands for the same or different perfluorinated aliphatic or aromatic radicals, in particular for perfluoroisopropyl or perfluoro tert-butyl, and
• L 2 and L 3 can be connected to one another.
• L 2 and L 3 together can represent, in particular, acrylonitrile or 5-cyanopentenoate.
• L 2 and R can be connected to one another. In this case, L 2 and R together can represent in particular -CH 2 -CH 2 CO 2 Me.
• L 2 , L 3 and R can be connected to one another.
• L 2 , L 3 and R together can in particular represent MeO 2 C (CH 2 ) 2 - (CH) - (CH 2 ) CO 2 Me.
• the hydrogenation can be carried out in the presence of a rhodium-containing compound which is homogeneous with respect to the reaction mixture and is selected as a catalyst from the group consisting of
• R F stands for the same or different perfluorinated aliphatic or aromatic radicals, in particular for perfluoro-iso-propyl or perfluoro-tert-butyl.
• Such catalysts and their preparation can be carried out by processes known per se, as described, for example, in EP-A-475 386, JACS 1991, 113, 2777-2779, JACS 1994, 116, 8038-8060.
• the hydrogenation according to the present process can advantageously be carried out at a hydrogen partial pressure in the range from 0.1 to 200 bar.
• the average mean residence time of the monoolefinically unsaturated compound, which bears at least two functional groups, independently of one another selected from the group consisting of nitrile group, carboxylic acid group, carboxylic acid ester group, carboxamide group is in the range from 0.1 to 100 hours proven advantageous.
• a temperature in the range from 30 ° C. to 160 ° C. is preferably suitable for the hydrogenation.
• HBAr F 4 required to activate the catalyst was prepared according to M. Brookhart, B. Grant, AF Volpe Organometallics 1992, 11, 3920-3922. HBAr F 4 denotes the bis-etherate of tetrakis [3,5-bis (trifluoromethyl) phenyl] boric acid.
• the analysis of the reaction outputs was carried out by means of GC (device: Hewlett Packard 5820; column: HP-5; length: 30 m; diameter: 0.25 mm; film thickness: 1.0 ⁇ m), the structure of the products being clarified beforehand by means of GC / MS coupling took place. All figures in area percent.
• Example 2 Analogously to Example 1, 60 ml (0.204 mmol) of Cp * Rh (C 2 H 4 ) 2 were first mixed with 120 ml of methyl acrylate in a suitable reaction vessel and then with a stoichiometric amount (based on Rh) of the acid HBAr F 4 at room temperature. 500 ppm of phenothiazine was added to the mixture as a polymerization inhibitor. The mixture was heated to 80 ° C. and stirred under a bar of hydrogen with a gassing stirrer. After 53 hours the pressure was increased from 1 bar to 5 bar H 2 . After certain times, samples were taken for gas chromatographic analysis (see Table 2). The 100% missing portion consists of methyl propionate and small amounts of branched dimers and trimers.
• reaction can also be carried out at 80 ° C., without solvent and in the presence of a further polymerization inhibitor (here phenothiazine).
• a further polymerization inhibitor here phenothiazine
• Example 2 Analogously to Example 1, 60 ml (0.204 mmol) of Cp * Rh (C 2 H 4 ) 2 were first mixed with 120 ml of methyl acrylate in a suitable reaction vessel and then with a stoichiometric amount (based on Rh) of the acid HBAr F 4 at room temperature. The mixture was heated to 80 ° C. and stirred under a bar of hydrogen with a gassing stirrer. After certain times, samples were taken for gas chromatographic analysis (see Table 3).
• the 100% missing portion consists of methyl propionate and small amounts of branched dimers and trimers.
• the example shows that the reaction can also be carried out at 80 ° C. without a polymerization inhibitor.

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