Title of Invention	PROCESS FOR PREPARING VINYL CARBOXYLATES
Abstract	Abstract The present invention relates to a process for preparing vinyl carboxylates, wherein a carboxylic acid is reacted with an alkyne compound in the presence of a catalyst which is selected from carbonyl complexes, halides and oxides of rhenium, of manganese, of tungsten, of molybdenum, of chromium and of iron and rhenium metal at a temperature of < 300X. The process gives the desired vinyl esters with high yield.

Title of Invention

PROCESS FOR PREPARING VINYL CARBOXYLATES

Abstract

Abstract The present invention relates to a process for preparing vinyl carboxylates, wherein a carboxylic acid is reacted with an alkyne compound in the presence of a catalyst which is selected from carbonyl complexes, halides and oxides of rhenium, of manganese, of tungsten, of molybdenum, of chromium and of iron and rhenium metal at a temperature of < 300X. The process gives the desired vinyl esters with high yield.

Full Text	Process for preparing vinyl carboxylates The present invention relates to a process for preparing vinyl carboxylates by reacting a carboxylic acid with an alkynes. The addition of carboxylic acids to alkynes to prepare the corresponding vinyl carboxylates has been known for some time. Suitable catalysts used are especially zinc salts, such as the zinc salt of the carboxylic acid taking part in the reaction; see, for example, US 2,066,075, US 3,455,998 and US 3,607,915. Since the zinc salts have only low selectivity and stability, attempts have been made to use other catalysts. For instance, US 5,430,179 describes the use of ruthenium complexes soluble in the reaction medium with a phosphates lagans. EP 512 656 A describes a process for preparing vinyl derivatives of Bromated acids, such as carboxylic acids, by reacting the Bronte acid with an acetylenically unsaturated compound in the presence of a ruthenium catalyst which is applied to an inter porous support. J. Org. Chem. 2004, 69, 5782-5784 describes the reaction of terminal alkynes with acetic acid or benzoic acid using Re(C0)5Br as the catalyst. It has been found that the anti-Markovnikov adduct is obtained with high selectivity especially in n-heptane’s and toluene as solvents. Organometallics 2000, 19, 170-183 describes the intramolecular hydroamination of aminoalkyne compounds using [Re(CO)5(H20)]BF4 as a catalyst. However, only a low yield is obtained. It is common to the prior art process that the yield of vinyl esters is not satisfactory. It is therefore an object of the present invention to provide a process for preparing vinyl carboxylates which proceeds with high yield. Moreover, the process shall be performable at temperatures at which even the thermally labile carboxylic acids and vinyl carboxylates do not decompose. Finally, the process shall be performable with small amounts of catalyst in order to restrict the costs for the catalyst. It has now been found that, surprisingly, this object is achieved when the catalyst used is a carbonyl complex, a halide or oxide of rhenium, of manganese, of tungsten, of molybdenum, of chromium, of iron or rhenium metal. The present invention therefore provides a process for preparing vinyl carboxylates of the formula 1: in which a) R^ is H or -COO-CH=CH-R^ and n is 1, or b) R^ is Ci-Cao-aikyi, C2-C2o-alkenyl, Cs-Cr-cycloalkyl, and n is 1, 2, 3 or 4, where R"" is optionally substituted by 1, 2 or 3 radicals which are each independently selected from phenyl, halogen, hydroxy, Ci-C4-alkoxy, amino, mono-Ci-C4-alkyl-amino, di-Ci-C4-alkylamino, -OCOR^ -COOR^ -CONR^R^ -NR^COR^ -OCONR^R^ or -NR'^COOR^ or c) R^ is aryl and n is 1, 2, 3, 4, 5 or 6, where aryl is optionally substituted by 1, 2 or 3 radicals which are each independently selected from Ci-C4-alkyl, halogen, hydroxy Ci-C4-alkoxy, amino, mono-Ci-C4-a!kylamino, di-Ci-C4-alkylamino, -OCOR^ -COOR^ -CONR'R^ -NR^COR^ -OCONR^R^ or -NRCOOR^ or d) R^ is bicycloalkyi having from 6 to 9 or from 7 to 9 carbon atoms or bicycloalkenyl having from 6 to 9 or from 7 to 9 carbon atoms and one or two carbon-carbon double bonds, and n is 1 or 2, where the bicycloalkyi radical may be substituted by 1, 2, 3, 4, 5 or 6 radicals which are each independently selected from halogen or CrC4-alkyl, or e) R^ is five- or six-mamboed heterocyclyl which has one or two heteroatoms which are each independently selected from N, O and S, and n is 1, 2 or 3, where the heterocyclyl radical may be substituted by 1 or 2 radicals which are each independently selected from halogen or Ci-C4-alkyt; R^ is H, Ci-Ce-alkyI, phenyl-Ci-C4-alkyl, phenyl which is optionally substituted by 1 or 2 Ci-C4-alkyl groups, or Ca-CT-cycioalkyI; R^ is Ci-C4-alkyl; R"^ and R^, which may be the same or different, are each H or Ci-C4-alkyl; comprising the reaction of a compound of the formula II in which R^ is H, -COOH or as defined above under b) or c) and n is as defined above 3 with a compound of the formula III H-CE C-R^ (III) In which R^ is as defined above, in the presence of a catalyst which is selected from carbonyl complexes, oxides and halides of rhenium, of manganese, of tungsten, of molybdenum, of chromium and of iron and rhenium metal at a temperature of A preferred embodiment of the present invention is a process for preparing vinyl carboxylate compounds of the formula I: in which a) R^ is H or -COO-CH=CH-R^ and n is 1, b) R^ is Ci-C2o-alkyl, C2-C2o-alkenyl, Cs-Co-cycloalkyl, and n is 1, 2, 3 or 4, in particular 1, 2 or 3, where R^ is optionally substituted by 1 or 2 radicals which ; each independently selected from phenyl, halogen, hydroxy, Ci-C4-alkoxy, amino, mono-Ci-C4-alkylamino, di-Ci-CMIkylamino, -OCOR^ -COOR^ -CONR^R^ -NR^COR^ -OCONR^R^ or -NR^COOR^ or c) R^ is aryl and n is 1, 2, 3, 4, 5 or 6, where aryl is optionally substituted by 1, 2 radicals which are each independently selected from Ci-C4-alkyl, halogen, hydroxy Ci-C4-alkoxy, amino, mono-Ci-C4-alkylamino, di-Ci-C4-alkylamino, -OCOR^ -COOR^ -CONRR^ -NR^COR^ -OCONR^R^ or-NR^COOR^ or R^ is H, Ci-Cs-alkyI, phenyl-Ci-C4-alkyl, phenyl which is optionally substituted by 1 c Ci-C4-alkyl groups, or Cs-Cr-cycioalkyI; R^ is Ci-C4-alkyl; R" and R^ which may be the same or different, are each H or Crick-alkyl; comprising the reaction of a compound of the formula II in which R^ is H, -COOH or as defined above under b) or c) and n is as defined above with a compound of the formula ill H-C= C-R^ (111) in which R^ is as defined above, in the presence of a catalyst which is selected from carbonyl complexes, oxides and halides of rhenium, of manganese, of tungsten, of molybdenum, of chromium and of iron at a temperature of In a further preferred embodiment, the invention relates to a process for preparing vinyl carboxylate compounds of the formula I: in which a) R^ is H or -COO-CH=CH-R^ and n is 1, b) R^ is Ci-Cao-alkyI, C2-C2o-alkenyl, Cs-Cy-cycloalkyl, and n is 1, 2, 3 or 4, in particular 1, 2 or 3, where R^ is optionally substituted by 1 or 2 radicals which are each independently selected from phenyl, halogen and Ci-C4-alkoxy or c) R^ is aryl and n is 1, 2, 3, 4, 5 or 6, where aryl is optionally substituted by 1, 2 or 3 radicals which are each independently selected from Ci-C4-alkyl, halogen and Ci-C4-alkoxy; R^ is H, Ci-Cs-aikyl, phenyl-Ci-C4-alkyl, phenyl which is optionally substituted by 1 or 2 CrC4-alkyl groups, or Cs-Cy-cycloalkyI; by reacting a compound of the formula II in which R^ is H, -COOH or as defined above under b) or c) and n is as defined above with a compound of the formula 111 H-C= C-R^ (111) in which R^ is as defined above, in the presence of a catalyst which is selected from carbonyl complexes of rhenium, of manganese, of tungsten, of molybdenum, of chromium and of iron at a temperature of The alkyl groups may be straight-chain or branched alkyl groups having the carbon number specified. Examples of such alkyl groups are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-hexyl, n-dodecyl, etc. Examples of C2-C2o-alkenyl groups are vinyl, 1- or 2-propenyl, buten-1-yl, buten-2-yl and isobutenyl. Halogen means fluorine, chlorine, bromine or iodine. Examples of Cs-Cz-cycloalkyl groups are cyclopropyl, cyciobutyl, cycloheptyl and especially cyclopentyl and cyclohexyl. Examples of bicycloalkyi groups are bicycled[2.1.1]hexane, bicycles[2.2.1]heptane, bicyclo[2.2.2]octane and bicyclo[2.3.2]nonane. Examples of bicycloalkenyl groups are bicyclo[2.2.1]heptene, bicyclo[2.2.2]octene and bicyclo[2.3.2]novena. Heterocyclyl may be aromatic or saturated or unsaturated nonaromatic heterocyclyl. Examples of aromatic heterocyclyl are pyridyl, pyrimidyl, triazinyl, pyrrolyl, furyl, thienyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, thiadiazolyl or triazyl. Examples of saturated heterocyclyl are pyrrolidinyl, tetrahydro-furanyl, piperidinyl, morpholinyl or piperazinyl. Aryl means preferably phenyl or naphthyl. When R^ has the above-specified definition b), n is preferably 1 or 2. When R^ has the above-specified definition c), n is preferably 1, 2 or 3. The catalyst used comprises the carbonyl complexes, oxides or halides of rhenium, of manganese, of tungsten, of molybdenum, of chromium and of iron. Carbonyl complexes are understood here to mean compounds which have at least one carbonyl group as a ligand. The remaining coordination sites can be occupied by other ligands as listed by way of example in the paragraph below. Oxides and halides are also understood to mean compounds in which one or more coordination sites and/or valences are occupied by a CrCs-alkyl group, and also oxyhalides. Examples thereof are CHsReOa, ReOaCi, or ReOCU. The catalysts may be present in all oxidation states; in the case of carbonyl complexes, they are preferably present in the 0 or I oxidation state. Preferred catalysts are the carbonyl complexes, oxides or halides of rhenium, of manganese or of molybdenum and especially of rhenium, the carbonyl complexes of rhenium or of manganese having been found to be particularly suitable. Particularly effective carbonyl complexes are those of the abovementioned metals. One or more of the carbonyl groups may be replaced by suitable ligands such as H2O, halogens, especially chlorine or bromine, phosphine ligands such as triphenylphosphine, trimethylphosphine, triethylphosphine, tri-n-butylphosphine, diphenylphosphinoethane, diphenylphosphinopropane, diphenylphosphinobutane, diphenylphosphinoferrocene, etc., amine ligands such as NH3, ethylenediamine, etc., alcohol ligands such as phenol, methanol, ethanol, etc., thio ligands such as methyl mercaptan or thiophenol. Examples of suitable carbonyl complex catalysts are Mn2(CO)io, Fe(C0)5, Fe2(CO)9, Mo(CO)6, W(CO)6 and Cr(C0)6. Particularly suitable catalysts have been found to be the rhenium catalysts. Examples thereof are Re2(CO)io,, Re(C0)5CI, Re(C0)5Br, ReBr(CO)3(CH3CN)2, ReCp(CO)3, Re(pentamethyl-Cp)(C0)3, ReCI(CO)3(CH3CN)2, ReBr(CO)3(THF)2, ReCp2, ReCI(CO)3(THF)2, Rez (pentamethyl-Cp)2(CO)3, Re2(pentamethyl-Cp)204, Re(pentamethyl-Cp)0Cl2 (Cp = cyclopentadiene; THF = tetrahydrofuran), Re207, Re, ReCIs, ReBrs and ReCHaOs. A particularly preferred catalyst is Re2(CO)io. The reaction can be effected in homogeneous or heterogeneous liquid phase. When a homogeneous liquid phase is desired, a catalyst is used which is soluble in the reaction medium under the given reaction conditions or goes into solution during the reaction. Such catalysts are in particular the carbonyl complexes of the metals which are useful here. Heterogeneous catalysts are the halides and oxides of these metals, and rhenium metal. The heterogeneous catalysts can be used directly, for example in powder form, or applied to a support. Suitable supports are carbon powder, zeolites, aluminum oxides silicon oxides, etc. In general, the catalyst is used in an amount of from 0.000005 to 1 mol%, preferably from 0.000005 to 0.5 mol%, more preferably from 0.00001 to 0.1 mol% and in particular from 0.00005 to 0.05 mol%, from 0.0001 to 0.05 mol%, from 0.0005 to 0.01 mol% or from 0.001 to 0.01 mol%, based in each case on equivalents of the compound of the formula II. The expression "equivalents" relates here to carboxyl groups of the formula II which can react with the compound of the formula III. Suitable starting compounds of the formula II are aliphatic monocarboxylic acids. Examples of such carboxylic acids are formic acid, acetic acid, halogenated carboxylic acids, such as chloroacetic acid or trifluoroacetic acid, propionic acid, aminocarboxylic acids, such as alanine, lactic acid or butyric acid, hydroxycarboxylic acids, such as hydroxybutyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, 2-methylpropionic acid, 2-methylbutyric acid, 3-methylbutyric acid, 2-methylpentanolc acid, 2-ethylhexanoic acid, 2-propylheptanoic acid, tertiary carboxylic acids of the formula R^R^C(CH3)C00H in which R® and R^ are each independently Ci-Ci2-alkyl, such as pivalic acid, 2,2-dimethylbutyric acid, 2,2-dimethylpentanoic acid, 2,2-dimethylhexanoic acid, 2,2-dimethylheptanoic acid, 2,2-dimethyloctanoic acid (Versatic acids 6, 7, 8, 9, 10), neononanoic acid, neodecanoic acid, neotridecanoic acid, stearic acid, oleic acid, lauric acid, palmitic acid, cyclohexanemono- and cyclohexanepolycarboxylic acids such as cyclohexane-carboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,3-dicarbpxylic acid, cyclohexane-1,4-dicarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid or phenylacetic acid. Suitable starting compounds of the formula II are also aliphatic polycarboxylic acids, especially dicarboxylic acids, and the derivatives of the polycarboxylic acids which have been partly esterified with a Ci-C4-alkanol and partly amidated with ammonia, a Ci-C4-monoalkylamine or a di-Ci-C4-alkylamine. Examples of aliphatic polycarboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, agaricicacid, 1,2,3-propanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, citric acid, malic acid, tartaric acid, glutamic acid, maleic acid and fumaric acid, particular preference being given to the use of adipic acid. Suitable starting compounds of the formula II are also bicyclic mono- and dicarboxylic acids such as Suitable starting compounds of tine formula II are also heterocyclic mono- and polycarboxylic acids and the derivatives of the polycarboxylic acids which have been partly esterified with a Ci-C4-alkanol and partly amidated with ammonia, a Ci-C4-mono-alkylamine or a di-Ci-C4-alkylamine. Examples thereof are 2-pyridinecarboxyiic acid, 3-pyridinecarboxylic acid or 4-pyridinecarboxylic acid, pyridinedicarboxylic acids such as 2,3- and 2,4-pyridinedicarboxylic acid, furan-2-carboxylic acid, furan-3-carboxylic acid, thiophene-2-carboxylic acid, thiophene-3-carboxylic acid or proline. Suitable starting compounds of the formula II are also aromatic monocarboxylic acids and polycarboxylic acids and the derivatives of the polycarboxylic acids which have been partly esterified with a Ci-C4-alkanol and partly amidated with ammonia, a Ci-C4-monoalkylamine or a di-Ci-C4-alkylamine. Examples of such carboxylic acids are benzoic acid, 2-, 3- or 4-methylbenzoic acid, salicylic acid, 2-, 3- or 4-aminobenzoic acid, 4-dimethylaminobenzoic acid, phthalic acid, isophthalic acid or terephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylicacid, 1,3,5-benzenetri-carboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,3,4-benzenetetracarboxylic acid, benzenepentacarboxylic acid and benzenehexacarboxylic acid, and tine derivatives of \he polycarboxylic acids which have been partly esterified with a Ci-C4-alkanol. The starting compounds of the formulae II and III are commercially available or irreparable by known processes. The above-described bicyclic carboxylic acids are obtainable by Diels-Alder reaction of cyclopentadiene, cyclohexadiene or cycloheptadiene with acrylic acid, maleic acid or fumaric acid, and if appropriate hydrogenation to the saturated mono- and dicarboxylic acids. Suitable starting compounds of the formula III are, for example, acetylene, propyne, 1-butyne, 1-pentyne, 1-hexyne and phenylacetylene, particular preference being given to using acetylene. The quantitative ratio of compound of the formula 11 to compound of the formula 111 can be selected within a wide range. In general, though, an excess of compound of the formula III is used, especially an excess of from 0.1 to 20 mol%, based on the compound of the formula II. The reaction is generally carried out in a suitable inert solvent. If the compound of the formula II is liquid at the temperature employed, it is possible to dispense with a solvent. Suitable inert solvents are aliphatic and aromatic hydrocarbons such as pentane, hexane, heptane, decalin, paraffin oil, toluene, xylene, etc., ethers such as tetrahydrofuran, dioxane or diphenyl ether, chlorinated hydrocarbons such as methylene chloride, 1,2-dichloroethane or chlorobenzene, esters such as ethyl acetate, n-butyl acetate or butyrolactone, acetonitrile, dimethylformamide, dim ethyl sulfoxide, N-methylpyrrolidone or polyethylene glycols or mixtures thereof. The reaction can also be performed in a compound of the formula 1 as a solvent if it is liquid at the selected reaction temperature. The reaction temperature can be selected freely within a wide range. It is generally selected such that there is rapid conversion without starting compounds or the products decomposing. It is appropriately The reaction is typically carried out under pressure, preference being given to establishing from 1 to 30 bar (absolute), preferably from 2 to 20 bar and in particular from 5 to 25 bar or from 10 to 20 bar. The pressure may, for example, be established with the compound of the formula III employed and/or an inert gas such as nitrogen. The reaction time is generally in the range from 0.5 to 72 hours, especially from 1 to 48 hours. If appropriate, it is also possible to add reaction-promoting additives such as zinc acetate, lithium salts, for example LiCI, Lewis acids such as BF3, etc., Lewis bases such as triethylamine, pyridine, 1,5-diazabicyclo[4.3.0]non-5-ene, etc., substances which react with the catalyst on CO and can thus create free coordination sites, for example trimethylamino N-oxide. The reaction can be carried out batchwise, continuously or in a semibatchwise process. The workup is effected in a customary manner, appropriately by distilling off the desired vinyl carboxylates. The catalyst remains in the bottoms and can be reused if appropriate. Appropriately, the reaction and the workup, especially the purifying distillation, can be carried out in the presence of a polymerization inhibitor. The polymerization inhibitors used may, for example, be hydroquinone, hydroquinone monomethyl ether, 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, nitroso compounds such as isoacryloyi nitrate, nitrosodiphenylamine, N-nitrosocyclohexyl-hydroxyamine, methylene blue, phenothiazine, tannic acid or diphenylamine. The polymerization inhibitors are used generally in amounts of from 1 to 10 000 ppm, especially of from 100 to 1000 ppm, based in each case on the overall mixture. The reaction proceeds selectively, i.e., even in the presence of other vinylatable groups in the compound of the formula II, such as OH or NH2, only the carboxyl groups are tinplated. If a compound of the formula II is used which, as well as the carboxyl group(s), also comprises another vinyl table group, the reaction temperature is appropriately selected within the range from 70 to 160°C and/or the reaction time within the range from 0.5 to 12 hours. A preferred embodiment of the invention relates to the reaction of the compounds of the formula II in which R^ is H, Ci-Ce-alkyI, Cs-Cz-cycloalkyl or phenyl, where the alkyl group may be substituted as specified above under b) and the phenyl group as specified above under c), and n is 1 with acetylene. A further preferred embodiment relates to the reaction of the compounds of the formula II in which R^ is CO2H and n is 1, or in which R^ is Ci-C2o-alkyl, especially Ci-C4-a!kyl, where R^ may be substituted as specified under b) above, and n is 2, with acetylene. Preference is given to carrying out this reaction at a temperature in the range from 70 to 220°C, preferably from 130°C to 220°C, in particular from 140 to 180°C or from 150 to IZCC. Catalyst is used especially in an amount of from 0.00001 to 0.1 mol%, especially from 0.0001 to 0.01 mol%, based on equivalents of dicarboxylic acid. The reaction of adipic acid with acetylene is particularly preferred. A further preferred embodiment relates to the reaction of the compounds of the formula II in which R^ is phenyl which may be substituted as defined under c) above, and n is 2, 3, 4, 5 or 6, especially 2 or 3, with acetylene. Preference is given to carrying out this reaction at a temperature in the range from 140 to 230°C, in particular from 150 to 200°C. The catalyst is used preferably in an amount of from 0.00001 to 0.1 mol%, especially from 0.0001 to 0.01 mol%, based on equivalents of polycarboxylic acid. The present invention also provides compounds of the formula I in which R^ is aryl and n is 2, 3, 4, 5 or 6, where aryl is optionally substituted by 1, 2 or 3 radicals which are each independently selected from Ci-C4-alkyl, halogen, Ci-C4-alkoxy, amino, mono-Ci-C4-alkylamino, di-Ci-C4-alkylamino, -OCOR^, -COOR^ -CONR^R^ -NR'COR^ -OCONR^R^ or -NR^COOR^ or Ri is Ca-Cy-cycloalkyI and n is 2 or 3, and R^ is H, d-Cs-alkyl, phenyl-Ci-C4-alkyl, phenyl which is optionally substituted by 1 or 2 Ci-C4-alkyl groups, or Cs-Cz-cycloalkyl. Particular preference is given to the preparation of divinely phthalate, divinely terephthalate and divine isophthalate, and also of divinely cyclohexane-1,2, divinely cyclohexane-1,3 and divinely cyclohexane-1,4, vinyl pyridine-2-carboxylate, vinyl pyridine-3-carboxylate and vinyl pyridine-4-carboxylate, and also vinyl negotiate. The present invention also provides the compounds of the formula I in which R^ is bicycloalkyi having from 6 to 9 carbon atoms or bicycloalkenyl having from 6 to 9 carbon atoms and one or two carbon-carbon double bonds and n is 1 or 2, or in which R^ is five- or six-mamboed heteroalkyi which has one or two heteroatoms which are each independently selected from N, O and S, where n is 1, 2 or 3; and R^ is H, Ci-Cs-alkyi, phenyl-Ci-C4-alkyi, phenyl which is optionally substituted by 1 or 2 Ci-C4-alkyi groups, or Ca-Cr-cycloalkyl. The vinyl esters obtainable by the process according to the invention are suitable for use in materials which can be cured thermally or by energy-rich radiation. The materials may be used as or in coating compositions, for example lacquers, printing inks or adhesives, as printing plates, as moldings, for producing photoresists, in stereolithography or as a casting material, for example for optical lenses. Substrates for the coating may, for example, be textile, leather, metal, plastic, glass, wood, paper or paperboard. The compounds of the formula I are usable as crosslinking agents in free-radical and cationic polymerizations. They are preferably used in UV-curable coatings, for example as reactive diluents. The examples which follow illustrate the invention without restricting it. The GC analyses (GC: gas chromatography) were effected on a capillary column with a Carbowax (polyethylene glycol) film, for example DB Wax from J & W Scientific. Examples Example 1 A mixture of 36.0 g of benzoic acid (295 mom), 0.25 g of Re2(CO)io (0.38 moll) and 78.0 g of toluene were subjected to veneration at 140°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. The yield determined by GC analysis was 99%. Example 2 A mixture of 8.0 g of adipic acid (55 mmol), 0.10 g of Re(C0)5CI (0.28 mmol) and 17.3 g of toluene was subjected to vinylation at 140°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. The yield determined by GC analysis was 96%. Example 3 A mixture of 8.0 g of adipic acid (55 mmol), 0.10 g of Re(C0)5Br (0.25 mmol) and 17.3 g of toluene was subjected to vinylation at 140°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. The yield determined by GC analysis was 95%. Example 4 A mixture of 36.0 g of adipic acid (247 mmol), 0.10 g of Re2(CO)io (0.15 mmol) and 78.0 g of toluene were subjected to vinylation at 140°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. The yield determined by GC analysis was 98%. Example 5 A mixture of 300.0 g of adipic acid (2.045 mol), 1.00 g of Re2(CO)io (1.50 mmol) and 700.0 g of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. The disillusive workup of the reaction mixture in the presence of a polymerization inhibitor afforded the divines ester of the carboxylic acid in a yield of 87%. Example 6 A mixture of 100.0 g of adipic acid (681.6 mol) and 0.50 of Re2(CO)io (0.75 mmol) was heated to 200°C without solvent for 2 h. After cooling to 160°C, the mixture was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h to obtain divinyl adipate. Example 7 A mixture of 8.0 g of terephthalic acid (48 mmol), 0.10 g of Re2(CO)io (0.15 mmol) and 17.3 g of toluene was subjected to vinylation at 140°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. Divinyl terephthalate was obtained, which was detectable by means of GC-MS analysis. Example 8 A mixture of 30.0 g (259 mmol) of fumaric acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 8 h. Divinyl fumarate was detected as the main product by means of GC-MS and GC analysis. Example 9 A mixture of 30.0 g (181 mmol) of phthalic acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 12 h. Divinyl phthalate was detected as the main product by means of GC-MS and GC analysis. Example 10 A mixture of 30.0 g (181 mmol) of isophthalic acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 20 h. Divinyl isophthalate was detected as the main product by means of GC-MS and GC analysis. Example 11 A mixture of 30.0 g (197 mmol) of 4-methoxybenzoic acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 18 h. Vinyl 4-methoxybenzoate was detected as the main product by means of GC-MS and GC analysis. Example 12 A mixture of 30.0 g (326 mmol) of pivalic acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 7 h. Vinyl pivalate was detected as the main product by means of GC-MS and GC analysis. Example 13 A mixture of 30.0 g (348 mmol) of crotonic acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. Vinyl crotonate was detected as the main product by means of GC-MS and GC analysis. Example 14 A mixture of 30.0 g (184 mmol) of 4-dimethylaminobenzoic acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. Vinyl 4-dimethylamino-benzoate was detected as the main product by means of GC-MS and GC analysis. Example 15 A mixture of 30.0 g (192 mmol) of 4-chlorobenzoic acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 20 h. Vinyl 4-chloroben2oate was detected as the main product by means of GC-MS and GC analysis. Example 16 A mixture of 30.0 g (417 mmol) of acrylic acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 140°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 17 h. Vinyl acrylate was detected as the main product by means of GC-MS and GC analysis. Example 17 A mixture of 30.0 g (149 mmol) of 4-bromobenzoic acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 4 h. Vinyl 4-bromobenzoate was detected as the main product by means of GC-MS and GC analysis. Example 18 A mixture of 30.0 g (348 mmol) of methacrylic acid, 0.5 g of Re2(CO)io (0.77 mmol) and so ml of toluene was subjected to vinylation at 140°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 13 h. Vinyl methacrylate was detected as the main product by means of GC-MS and GC analysis. Example 19 A mixture of 40.0 g (241 mmol) of terephthalic acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 175°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 2 h. Divinyl terephthalate was detected as the main product by means of GC-MS and GC analysis. Example 20 A mixture of 40.0 g (345 mmol) of humanoid acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 1 h. Vinyl emanate was detected as the main product by means of GC-MS and GC analysis. Example 21 A mixture of 40.0 g (313 mmol) of cyclohexanoic acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 3.5 h. Vinyl cyclohexanoate was detected as the main product by means of GC-MS and GC analysis. Example 22 A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re2(CO)io (0.12 mmol) and 100 ml of xylene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 24 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis. Example 23 A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re2(CO)io (0.12 mmol) and 100 ml of dioxane was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 2 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis. Example 24 A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re2(CO)io (0.12 mmol) and 100 ml of THF was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 1 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis. Example 25 A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re2(CO)io (0.12 mmol) and 100 ml of NMP was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 2.5 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis. Example 26 A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re2(CO)io (0.12 mmol) and 100 ml of diphenyl ether was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 2 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis. Example 27 A mixture of 6.5 g (253 mmol) of adipic acid, 0.08 g of Re2(CO)io (0.12 mmol) and 100 ml of decalin was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 10 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis. Example 28 A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re2(CO)io (0.12 mmol) and 100 ml of paraffin oil was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 12 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis. Example 29 A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re2(CO)io (0.12 mmol) and 100 ml of acetonitrile was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 12 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis. Example 30 A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re2(CO)io (0.12 mmol) and 100 ml of butyrolactone was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 26 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis. Example 31 A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re2(CO)io (0.12 mmol) and 100 ml of divinyl adipate was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 24 h. Divinyl adipate was detected as tlie main product by means of GC-MS and GC analysis. Example 32 A mixture of 36.5 g (253 mmol) of adipic acid, 0.05 g of Re207 (1.03 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis. Example 33 A mixture of 8.0 g (56 mmol) of adipic acid, 0.10 g of rhenium powder (0.54 mmol) and 20 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. Divinyl adipate was detected by means of GC analysis. Example 34 A mixture of 36.5 g (253 mmol) of adipic acid, 0.073 g of ReCb (0.25 mmol) and 100 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 30 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis. Example 35 A mixture of 36.5 g (253 mmol) of adipic acid, 0.062 g of ReCHsOs (0.25 mmol) and 100 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 30 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis. Example 36 A mixture of 36.5 g (253 mmol) of adipic acid, 5.0 g of Re207 on Si02/Al203 (3% Re, 0.8 mmol) and 100 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 5 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis. Example 37 A mixture of 18.25 g (127 mmol) of adipic acid, 0.021 g of Re2(CO)io (0.03 mmol) and 60 ml of divinyl adipate was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 7 bar for 9.5 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis. Example 38 A mixture of 18.25 g (127 mmol) of adipic acid, 0.021 g of Re2(CO)io (0.03 mmol) and 60 ml of divinyl adipate was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 4 bar for 8 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis. Example 39 A mixture of 18.25 g (127 mmol) of adipic acid, 0.021 g of Re2(CO)io (0.03 mmol) and 60 ml of divinyl adipate was subjected to vinylation at 160°C, a nitrogen pressure of 1 bar and an acetylene pressure of 3 bar for 11 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis. Example 40 A mixture of 40.0 g (181 mmol) of cyclohexane-1,4-dicarboxylic acid, 0.05 g of Re2(CO)io (0.08 mmol) and 90 ml of dioxane was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 5 h. Divinyl cyclohexane-1,4-dicarboxylate was detected as the main product by means of GC-MS and GC analysis. Example 41 A mixture of 8.0 g (55 mmol) of adipic acid, 1.33 g of Mn2(CO)io (3.4 mmol) and 20 ml of dioxane was subjected to vinylation at 140°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. Divinyl adipate was detected by means of GC analysis. Example 42 A mixture of 12.0 g (82 mmol) of adipic acid, 2.00 g of Mo(CO)6 (7.6 mmol) and 30 ml of toluene was subjected to vinylation at 150°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6.5 h. Divinyl adipate was detected by means of GC analysis. Example 43 A mixture of 8.0 g (55 mmol) of adipic acid, 1.33 g of Fe(C0)5 (6.8 mmol) and 20 ml of toluene was subjected to vinylation at 140°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6.0 h. Divinyl adipate was detected by means of GC analysis. Example 44 A' mixture of 40.0 g (171 mmol) of butanetetracarboxylic acid, 50 mg of Re2(CO)io (0.08 mmol) and 80 g of xylene (isomer mixture) was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 14.0 h. Tetravinyl butanetetracarboxylate was detected by means of MS analysis. Example 45 A mixture of 10.0 g (55 mmol) of norbornenedicarboxylic acid, 50 mg of Re2(CO)io (0.08 mmol) and 80 g of xylene (isomer mixture) was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 4.0 h. Divinyi Norborne ate was detected by means of GC analysis. Example 46 A mixture of 15.0 g (46 mmol) of 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid (Het acid), 50 mg of Re2(CO)io (0.08 mmol) and 15 g of xylene (isomer mixture) was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6.0 h. Het acid divinyi ester was detected by means of GC-MS analysis. Example 47 A mixture of 45.0 g (308 mmol) of adipic acid, 100 mg of Re2(CO)io (0.153 mmol) and 105 g of xylene (isomer mixture) was subjected to vinylation at 200°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 9 h. Divinyi adipate was detected as the main product by means of GC analysis. Example 48 A mixture of 7.5 g (51 mmol) of adipic acid, of 100 mg of Re2(CO)io (0.153 mmol) and 142.5 g of xylene (isomer mixture) was subjected to vinylation at 240°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 9 h. Divinyi adipate was detected as the main product by means of GC analysis. What is claimed is: 1. A process for preparing vinyl carboxylate compounds of the formula I: in which a) R^ is H or -C00-CH=CH-R2 and n is 1, b) R^ is Ci-C2o-alkyl, Ca-Cao-aikenyl or Cs-Cr-cycioaikyl, and n is 1, 2, 3 or 4, where R^ is optionally substituted by 1, 2 or 3 radicals which are each independently selected from phenyl, halogen, hydroxy, CrC4-alkoxy, amino, mono-Ci-C4-alkylamino, di-Ci-C4-alkylamino, -OCOR^ -COOR^, -CONR^R^ -NR^COR^ -OCONR^R^ or -NR^COOR^ or c) R^ is aryl and n is 1, 2, 3, 4, 5 or 6, where aryl is optionally substituted by 1, 2 or 3 radicals which are each independently selected from Ci-C4-alkyl, halogen, hydroxy, Ci-C4-alkoxy, amino, mono-Ci-C4-alkylamino, di-Ci-C4-alkylamino, -OCOR^ -COOR^ -CONRR^ -NR^COR^ -OCONR^R^ or -NR^COOR^ or d) R^ is bicycloalkyi having from 7 to 9 carbon atoms or bicycloalkenyl having from 7 to 9 carbon atoms and one or two carbon-carbon double bonds, and n is 1 or 2, where the bicycloalkyi radical may be substituted by 1, 2, 3, 4, 5 or 6 radicals which are each independently selected from halogen or C1-C4-alkyl, or e) R^ is five- or six-membered heterocyclyl which has one or two heteroatoms which are each independently selected from N, O and S, and n is 1, 2 or 3, where the heterocyclyl radical may be substituted by 1 or 2 radicals which are each independently selected from halogen or Ci-C4-alkyl; R^ is H, Ci-Cs-alkyI, phenyl-Ci-C4-alkyl, phenyl which is optionally substituted by 1 or 2 Ci-C4-alkyl groups, or Ca-Cj-cycloalkyl; R^ is Ci-C4-alkyl; R" and R^, which may be the same or different, are each H or Ci-C4-alkyl; comprising the reaction of a compound of the formula II in which R^ is H, -COOH or as defined above under b) or c) and n is as defined above with a compound of the formula III H-C= C-R^ (III) in which R^ is as defined above, in the presence of a catalyst which is selected from carbonyl complexes, oxides and halides of rhenium, of manganese, of tungsten, of molybdenum, of chromium and of iron and rhenium metal at a temperature of 2. The process according to claim 1, wherein the catalyst is selected from carbony complexes, oxides and halides of rhenium, of manganese and of molybdenum. 3. The process according to claim 2, wherein the catalyst used is Re2(CO)io. 4. The process according to any of the preceding claims, wherein the catalyst is used in an amount of from 0.000005 to 1 mor/o based on equivalents of the compound of the formula II. 5. The process according to any of the preceding claims, wherein the compound c the formula III is selected from acetylene, propyne, 1-butyne, 1-pentyne, 1-hexyne and phenylacetylene. 6. The process according to any of the preceding claims, wherein the compound c the formula II used is an aliphatic monocarboxylic acid. 7. The process according to claim 6, wherein the aliphatic monocarboxylic acid is selected from acetic acid, phenylacetic acid, propionic acid, alanine, butyric aci( hydroxybutyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, 2-methylpropionic acid, 2-methylbutyric acid, 3-methylbutyric acid, 2-methylpentanoic acid, 2-ethylhexanoic acid, 2-propyl-heptanoic acid, pivalic acid, 2,2-dimethylbutyric acid, 2,2-dimethylpentanoic acii 2,2-dimethylhexanoic acid, 2,2-dimethylheptanoic acid, 2,2-dimethyloctanoic acid, neononanoic acid, neodecanoic acid, neotridecanoic acid, stearic acid, ok acid, lauric acid, palmitic acid, cyclohexanecarboxylic acid, acrylic acid, methacrylic acid, crotonic acid and cinnamic acid. 8. The process according to any of claims 1 to 5, wherein the compound of the formula 11 used is an aliphatic polycarboxylic acid. 9. The process according to claim 8, wherein the aliphatic polycarboxylic acid is selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacicacid, agaric acid, 1,2,3-propanetricarboxylicacid, 1,2,3,4-butanetetra-carboxylic acid, cithc acid, malic acid, tartaric acid, glutamic acid, maleic acid and fumaric acid. 10. The process according to claim 9, wherein the compound of the formula II used is adipic acid. 11. The process according to any of claims 1 to 5, wherein the compound of the formula II used is a cycloaliphatic mono- or dicarboxylic acid. 12. The process according to claim 11, wherein the compound of the formula 11 used is cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,3-dicarboxyiic acid or cyclohexane-1,4-dicarboxylic acid. 13. The process according to any of claims 1 to 5, wherein the compound of the formula II used is a bicyclic or heterocyclic mono- or dicarboxylic acid. 14. The process according to claim 13, wherein the compound of the formula II used is a compound of the formula 15. The process according to claim 13, wlnerein ttie compound of the formula II used is 2-pyridinecarboxylic acid, 3-pyridinecarboxylic acid, 4-pyridinecarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, furan-2-carboxylic acid, furan-3-carboxylic acid, thiophene-2-carboxylic acid, thiophene-3-carboxylic acid or proline. 16. The process according to any of claims 8 to 15, wherein the reaction is carried out at a temperature in the range from 70 to 260°C. 17. The process according to any of claims 8 to 15, wherein the catalyst is used in an amount of from 0.000001 to 0.0025 mol%, based on equivalents of the compound of the formula II. 18. The process according to any of claims 1 to 5, wherein the compound of the formula II used is an aromatic monocarboxylic acid or an aromatic polycarboxylic acid. 19. The process according to claim 18, wherein the compound of the formula II used is benzoic acid, 2-, 3- or 4-methylbenzoic acid, salicylic acid, 2-, 3- or 4-aminoben2oic acid, 4-dimethylaminobenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetri-carboxyiic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,3,4-benzenetetracarboxylicacid, benzenepentacarboxylic acid or benzenehexacarboxyiic acid. 20. The process according to claim 18 or 19, wherein the reaction is carried out at a temperature in the range from 140 to 230°C. 21. The process according to any of the preceding claims, where the compound of the formula 111 is used in an excess of from 0.1 to 20 mol%, based on equivalents of the compound of the formula II. 22. The process according to any of the preceding claims, wherein the compound of the formula III used is acetylene. 23. A vinyl carboxylate of the formula 1 in which R"" is aryl and n is 2, 3, 4, 5 or 6, where aryl is optionally substituted by 1, 2 or 3 radicals which are each independently selected from Ci-C4-alkyl, halogen, Ci-C4-alkoxy, amino, mono- Ci-C4-alkylamino, di-Ci-C4-alkylamino, -OCOR^ -COOR^ -CONRR^ -NR^COR^ -OCONR^R^ or -NR^COOR^, or in which Ri is Cs-Cz-cycloalky! and n is 2 or 3; and R^ is H, Ci-Cs-alkyI, phenyl-Ci-C4-alkyl, phenyl which is optionally substituted by 1 or 2 Ci-C4-alkyl groups, or C3-C7-cycloalkyl. 24. The vinyl carboxylate according to claim 22 of the formula I in which R^ is H. 25. The vinyl carboxylate according to claim 24, namely divinyl cyclohexane- 1,2-dicarboxylate, divinyl cyclohexane-1,3-dicarboxylate or divinyl cyclohexane-1,4-dicarboxylate. 26. The vinyl carboxylate according to claim 25, namely divinyl cyclohexane- 1,4-dicarboxylate. 27. Tetravinyl butane-1,2,3,4-tetracarboxylate. ■ I 28. The vinyl carboxylate of the formula i: in which R^ is bicycloalkyi having from 6 to 9 carbon atoms or bicydoalkenyl having from 6 to 9 carbon atoms and one or two carbon-carbon double bonds and n is 1 or 2, or in which R^ is five- or six-membered heterocyclyl which has one or two heteroatoms which are each independently selected from N, O and S, where n is 1, 2 or 3; and R^ is H, Ci-Ce-aikyl, phenyl-Ci-C4-alkyl, phenyl which is optionally substituted by 1 or 2 Ci-C4-alkyl groups, or Ca-Cr-cycloalkyl. 29. The use of the vinyl carboxylates according to any of claims 23 to 28 as crosslinkers or reactive diluents.

Full Text

Process for preparing vinyl carboxylates
The present invention relates to a process for preparing vinyl carboxylates by reacting a carboxylic acid with an alkynes.
The addition of carboxylic acids to alkynes to prepare the corresponding vinyl carboxylates has been known for some time. Suitable catalysts used are especially zinc salts, such as the zinc salt of the carboxylic acid taking part in the reaction; see, for example, US 2,066,075, US 3,455,998 and US 3,607,915.
Since the zinc salts have only low selectivity and stability, attempts have been made to use other catalysts. For instance, US 5,430,179 describes the use of ruthenium complexes soluble in the reaction medium with a phosphates lagans. EP 512 656 A describes a process for preparing vinyl derivatives of Bromated acids, such as carboxylic acids, by reacting the Bronte acid with an acetylenically unsaturated compound in the presence of a ruthenium catalyst which is applied to an inter porous support. J. Org. Chem. 2004, 69, 5782-5784 describes the reaction of terminal alkynes with acetic acid or benzoic acid using Re(C0)5Br as the catalyst. It has been found that the anti-Markovnikov adduct is obtained with high selectivity especially in n-heptane’s and toluene as solvents. Organometallics 2000, 19, 170-183 describes the intramolecular hydroamination of aminoalkyne compounds using [Re(CO)5(H20)]BF4 as a catalyst. However, only a low yield is obtained.
It is common to the prior art process that the yield of vinyl esters is not satisfactory.
It is therefore an object of the present invention to provide a process for preparing vinyl carboxylates which proceeds with high yield.
Moreover, the process shall be performable at temperatures at which even the thermally labile carboxylic acids and vinyl carboxylates do not decompose.
Finally, the process shall be performable with small amounts of catalyst in order to restrict the costs for the catalyst.
It has now been found that, surprisingly, this object is achieved when the catalyst used is a carbonyl complex, a halide or oxide of rhenium, of manganese, of tungsten, of molybdenum, of chromium, of iron or rhenium metal.
The present invention therefore provides a process for preparing vinyl carboxylates of the formula 1:

in which
a) R^ is H or -COO-CH=CH-R^ and n is 1, or
b) R^ is Ci-Cao-aikyi, C2-C2o-alkenyl, Cs-Cr-cycloalkyl, and n is 1, 2, 3 or 4, where R"" is optionally substituted by 1, 2 or 3 radicals which are each independently selected from phenyl, halogen, hydroxy, Ci-C4-alkoxy, amino, mono-Ci-C4-alkyl-amino, di-Ci-C4-alkylamino, -OCOR^ -COOR^ -CONR^R^ -NR^COR^ -OCONR^R^ or -NR'^COOR^ or
c) R^ is aryl and n is 1, 2, 3, 4, 5 or 6, where aryl is optionally substituted by 1, 2 or 3 radicals which are each independently selected from Ci-C4-alkyl, halogen, hydroxy Ci-C4-alkoxy, amino, mono-Ci-C4-a!kylamino, di-Ci-C4-alkylamino, -OCOR^ -COOR^ -CONR'R^ -NR^COR^ -OCONR^R^ or -NR*COOR^ or
d) R^ is bicycloalkyi having from 6 to 9 or from 7 to 9 carbon atoms or bicycloalkenyl having from 6 to 9 or from 7 to 9 carbon atoms and one or two carbon-carbon double bonds, and n is 1 or 2, where the bicycloalkyi radical may be substituted by 1, 2, 3, 4, 5 or 6 radicals which are each independently selected from halogen or CrC4-alkyl, or
e) R^ is five- or six-mamboed heterocyclyl which has one or two heteroatoms which are each independently selected from N, O and S, and n is 1, 2 or 3, where the heterocyclyl radical may be substituted by 1 or 2 radicals which are each independently selected from halogen or Ci-C4-alkyt;
R^ is H, Ci-Ce-alkyI, phenyl-Ci-C4-alkyl, phenyl which is optionally substituted by 1 or 2 Ci-C4-alkyl groups, or Ca-CT-cycioalkyI;
R^ is Ci-C4-alkyl;
R"^ and R^, which may be the same or different, are each H or Ci-C4-alkyl;
comprising the reaction of a compound of the formula II

in which R^ is H, -COOH or as defined above under b) or c) and n is as defined above
3

with a compound of the formula III
H-CE C-R^ (III)
In which R^ is as defined above, in the presence of a catalyst which is selected from carbonyl complexes, oxides and halides of rhenium, of manganese, of tungsten, of molybdenum, of chromium and of iron and rhenium metal at a temperature of A preferred embodiment of the present invention is a process for preparing vinyl carboxylate compounds of the formula I:
in which
a) R^ is H or -COO-CH=CH-R^ and n is 1,
b) R^ is Ci-C2o-alkyl, C2-C2o-alkenyl, Cs-Co-cycloalkyl, and n is 1, 2, 3 or 4, in particular 1, 2 or 3, where R^ is optionally substituted by 1 or 2 radicals which ; each independently selected from phenyl, halogen, hydroxy, Ci-C4-alkoxy, amino, mono-Ci-C4-alkylamino, di-Ci-CMIkylamino, -OCOR^ -COOR^ -CONR^R^ -NR^COR^ -OCONR^R^ or -NR^COOR^ or
c) R^ is aryl and n is 1, 2, 3, 4, 5 or 6, where aryl is optionally substituted by 1, 2 radicals which are each independently selected from Ci-C4-alkyl, halogen, hydroxy Ci-C4-alkoxy, amino, mono-Ci-C4-alkylamino, di-Ci-C4-alkylamino, -OCOR^ -COOR^ -CONR*R^ -NR^COR^ -OCONR^R^ or-NR^COOR^ or
R^ is H, Ci-Cs-alkyI, phenyl-Ci-C4-alkyl, phenyl which is optionally substituted by 1 c Ci-C4-alkyl groups, or Cs-Cr-cycioalkyI;
R^ is Ci-C4-alkyl;
R" and R^ which may be the same or different, are each H or Crick-alkyl;
comprising the reaction of a compound of the formula II

in which R^ is H, -COOH or as defined above under b) or c) and n is as defined above with a compound of the formula ill
H-C= C-R^ (111)
in which R^ is as defined above, in the presence of a catalyst which is selected from carbonyl complexes, oxides and halides of rhenium, of manganese, of tungsten, of molybdenum, of chromium and of iron at a temperature of In a further preferred embodiment, the invention relates to a process for preparing vinyl carboxylate compounds of the formula I:

in which
a) R^ is H or -COO-CH=CH-R^ and n is 1,
b) R^ is Ci-Cao-alkyI, C2-C2o-alkenyl, Cs-Cy-cycloalkyl, and n is 1, 2, 3 or 4, in particular 1, 2 or 3, where R^ is optionally substituted by 1 or 2 radicals which are each independently selected from phenyl, halogen and Ci-C4-alkoxy or
c) R^ is aryl and n is 1, 2, 3, 4, 5 or 6, where aryl is optionally substituted by 1, 2 or 3 radicals which are each independently selected from Ci-C4-alkyl, halogen and Ci-C4-alkoxy;
R^ is H, Ci-Cs-aikyl, phenyl-Ci-C4-alkyl, phenyl which is optionally substituted by 1 or 2 CrC4-alkyl groups, or Cs-Cy-cycloalkyI;
by reacting a compound of the formula II

in which R^ is H, -COOH or as defined above under b) or c) and n is as defined above with a compound of the formula 111
H-C= C-R^ (111)

in which R^ is as defined above, in the presence of a catalyst which is selected from carbonyl complexes of rhenium, of manganese, of tungsten, of molybdenum, of chromium and of iron at a temperature of The alkyl groups may be straight-chain or branched alkyl groups having the carbon number specified. Examples of such alkyl groups are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-hexyl, n-dodecyl, etc.
Examples of C2-C2o-alkenyl groups are vinyl, 1- or 2-propenyl, buten-1-yl, buten-2-yl and isobutenyl.
Halogen means fluorine, chlorine, bromine or iodine.
Examples of Cs-Cz-cycloalkyl groups are cyclopropyl, cyciobutyl, cycloheptyl and especially cyclopentyl and cyclohexyl.
Examples of bicycloalkyi groups are bicycled[2.1.1]hexane, bicycles[2.2.1]heptane, bicyclo[2.2.2]octane and bicyclo[2.3.2]nonane.
Examples of bicycloalkenyl groups are bicyclo[2.2.1]heptene, bicyclo[2.2.2]octene and bicyclo[2.3.2]novena.
Heterocyclyl may be aromatic or saturated or unsaturated nonaromatic heterocyclyl. Examples of aromatic heterocyclyl are pyridyl, pyrimidyl, triazinyl, pyrrolyl, furyl, thienyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, thiadiazolyl or triazyl. Examples of saturated heterocyclyl are pyrrolidinyl, tetrahydro-furanyl, piperidinyl, morpholinyl or piperazinyl.
Aryl means preferably phenyl or naphthyl.
When R^ has the above-specified definition b), n is preferably 1 or 2. When R^ has the above-specified definition c), n is preferably 1, 2 or 3.
The catalyst used comprises the carbonyl complexes, oxides or halides of rhenium, of manganese, of tungsten, of molybdenum, of chromium and of iron. Carbonyl complexes are understood here to mean compounds which have at least one carbonyl group as a ligand. The remaining coordination sites can be occupied by other ligands as listed by way of example in the paragraph below. Oxides and halides are also understood to mean compounds in which one or more coordination sites and/or

valences are occupied by a CrCs-alkyl group, and also oxyhalides. Examples thereof are CHsReOa, ReOaCi, or ReOCU.
The catalysts may be present in all oxidation states; in the case of carbonyl complexes, they are preferably present in the 0 or I oxidation state. Preferred catalysts are the carbonyl complexes, oxides or halides of rhenium, of manganese or of molybdenum and especially of rhenium, the carbonyl complexes of rhenium or of manganese having been found to be particularly suitable.
Particularly effective carbonyl complexes are those of the abovementioned metals. One or more of the carbonyl groups may be replaced by suitable ligands such as H2O, halogens, especially chlorine or bromine, phosphine ligands such as triphenylphosphine, trimethylphosphine, triethylphosphine, tri-n-butylphosphine, diphenylphosphinoethane, diphenylphosphinopropane, diphenylphosphinobutane, diphenylphosphinoferrocene, etc., amine ligands such as NH3, ethylenediamine, etc., alcohol ligands such as phenol, methanol, ethanol, etc., thio ligands such as methyl mercaptan or thiophenol. Examples of suitable carbonyl complex catalysts are Mn2(CO)io, Fe(C0)5, Fe2(CO)9, Mo(CO)6, W(CO)6 and Cr(C0)6.
Particularly suitable catalysts have been found to be the rhenium catalysts. Examples thereof are Re2(CO)io,, Re(C0)5CI, Re(C0)5Br, ReBr(CO)3(CH3CN)2, ReCp(CO)3, Re(pentamethyl-Cp)(C0)3, ReCI(CO)3(CH3CN)2, ReBr(CO)3(THF)2, ReCp2, ReCI(CO)3(THF)2, Rez (pentamethyl-Cp)2(CO)3, Re2(pentamethyl-Cp)204, Re(pentamethyl-Cp)0Cl2 (Cp = cyclopentadiene; THF = tetrahydrofuran), Re207, Re, ReCIs, ReBrs and ReCHaOs. A particularly preferred catalyst is Re2(CO)io.
The reaction can be effected in homogeneous or heterogeneous liquid phase. When a homogeneous liquid phase is desired, a catalyst is used which is soluble in the reaction medium under the given reaction conditions or goes into solution during the reaction. Such catalysts are in particular the carbonyl complexes of the metals which are useful here. Heterogeneous catalysts are the halides and oxides of these metals, and rhenium metal. The heterogeneous catalysts can be used directly, for example in powder form, or applied to a support. Suitable supports are carbon powder, zeolites, aluminum oxides silicon oxides, etc.
In general, the catalyst is used in an amount of from 0.000005 to 1 mol%, preferably from 0.000005 to 0.5 mol%, more preferably from 0.00001 to 0.1 mol% and in particular from 0.00005 to 0.05 mol%, from 0.0001 to 0.05 mol%, from 0.0005 to 0.01 mol% or from 0.001 to 0.01 mol%, based in each case on equivalents of the compound

of the formula II. The expression "equivalents" relates here to carboxyl groups of the formula II which can react with the compound of the formula III.
Suitable starting compounds of the formula II are aliphatic monocarboxylic acids. Examples of such carboxylic acids are formic acid, acetic acid, halogenated carboxylic acids, such as chloroacetic acid or trifluoroacetic acid, propionic acid, aminocarboxylic acids, such as alanine, lactic acid or butyric acid, hydroxycarboxylic acids, such as hydroxybutyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, 2-methylpropionic acid, 2-methylbutyric acid, 3-methylbutyric acid, 2-methylpentanolc acid, 2-ethylhexanoic acid, 2-propylheptanoic acid, tertiary carboxylic acids of the formula R^R^C(CH3)C00H in which R® and R^ are each independently Ci-Ci2-alkyl, such as pivalic acid, 2,2-dimethylbutyric acid, 2,2-dimethylpentanoic acid, 2,2-dimethylhexanoic acid, 2,2-dimethylheptanoic acid, 2,2-dimethyloctanoic acid (Versatic acids 6, 7, 8, 9, 10), neononanoic acid, neodecanoic acid, neotridecanoic acid, stearic acid, oleic acid, lauric acid, palmitic acid, cyclohexanemono- and cyclohexanepolycarboxylic acids such as cyclohexane-carboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,3-dicarbpxylic acid, cyclohexane-1,4-dicarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid or phenylacetic acid.
Suitable starting compounds of the formula II are also aliphatic polycarboxylic acids, especially dicarboxylic acids, and the derivatives of the polycarboxylic acids which have been partly esterified with a Ci-C4-alkanol and partly amidated with ammonia, a Ci-C4-monoalkylamine or a di-Ci-C4-alkylamine. Examples of aliphatic polycarboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, agaricicacid, 1,2,3-propanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, citric acid, malic acid, tartaric acid, glutamic acid, maleic acid and fumaric acid, particular preference being given to the use of adipic acid.
Suitable starting compounds of the formula II are also bicyclic mono- and dicarboxylic acids such as

Suitable starting compounds of tine formula II are also heterocyclic mono- and polycarboxylic acids and the derivatives of the polycarboxylic acids which have been partly esterified with a Ci-C4-alkanol and partly amidated with ammonia, a Ci-C4-mono-alkylamine or a di-Ci-C4-alkylamine. Examples thereof are 2-pyridinecarboxyiic acid, 3-pyridinecarboxylic acid or 4-pyridinecarboxylic acid, pyridinedicarboxylic acids such as 2,3- and 2,4-pyridinedicarboxylic acid, furan-2-carboxylic acid, furan-3-carboxylic acid, thiophene-2-carboxylic acid, thiophene-3-carboxylic acid or proline.
Suitable starting compounds of the formula II are also aromatic monocarboxylic acids and polycarboxylic acids and the derivatives of the polycarboxylic acids which have been partly esterified with a Ci-C4-alkanol and partly amidated with ammonia, a Ci-C4-monoalkylamine or a di-Ci-C4-alkylamine. Examples of such carboxylic acids are

benzoic acid, 2-, 3- or 4-methylbenzoic acid, salicylic acid, 2-, 3- or 4-aminobenzoic acid, 4-dimethylaminobenzoic acid, phthalic acid, isophthalic acid or terephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylicacid, 1,3,5-benzenetri-carboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,3,4-benzenetetracarboxylic acid, benzenepentacarboxylic acid and benzenehexacarboxylic acid, and tine derivatives of \he polycarboxylic acids which have been partly esterified with a Ci-C4-alkanol.
The starting compounds of the formulae II and III are commercially available or irreparable by known processes. The above-described bicyclic carboxylic acids are obtainable by Diels-Alder reaction of cyclopentadiene, cyclohexadiene or cycloheptadiene with acrylic acid, maleic acid or fumaric acid, and if appropriate hydrogenation to the saturated mono- and dicarboxylic acids.
Suitable starting compounds of the formula III are, for example, acetylene, propyne, 1-butyne, 1-pentyne, 1-hexyne and phenylacetylene, particular preference being given to using acetylene.
The quantitative ratio of compound of the formula 11 to compound of the formula 111 can be selected within a wide range. In general, though, an excess of compound of the formula III is used, especially an excess of from 0.1 to 20 mol%, based on the compound of the formula II.
The reaction is generally carried out in a suitable inert solvent. If the compound of the formula II is liquid at the temperature employed, it is possible to dispense with a solvent. Suitable inert solvents are aliphatic and aromatic hydrocarbons such as pentane, hexane, heptane, decalin, paraffin oil, toluene, xylene, etc., ethers such as tetrahydrofuran, dioxane or diphenyl ether, chlorinated hydrocarbons such as methylene chloride, 1,2-dichloroethane or chlorobenzene, esters such as ethyl acetate, n-butyl acetate or butyrolactone, acetonitrile, dimethylformamide, dim ethyl sulfoxide, N-methylpyrrolidone or polyethylene glycols or mixtures thereof. The reaction can also be performed in a compound of the formula 1 as a solvent if it is liquid at the selected reaction temperature.
The reaction temperature can be selected freely within a wide range. It is generally selected such that there is rapid conversion without starting compounds or the products decomposing. It is appropriately
The reaction is typically carried out under pressure, preference being given to establishing from 1 to 30 bar (absolute), preferably from 2 to 20 bar and in particular from 5 to 25 bar or from 10 to 20 bar. The pressure may, for example, be established with the compound of the formula III employed and/or an inert gas such as nitrogen. The reaction time is generally in the range from 0.5 to 72 hours, especially from 1 to 48 hours.
If appropriate, it is also possible to add reaction-promoting additives such as zinc acetate, lithium salts, for example LiCI, Lewis acids such as BF3, etc., Lewis bases such as triethylamine, pyridine, 1,5-diazabicyclo[4.3.0]non-5-ene, etc., substances which react with the catalyst on CO and can thus create free coordination sites, for example trimethylamino N-oxide.
The reaction can be carried out batchwise, continuously or in a semibatchwise process. The workup is effected in a customary manner, appropriately by distilling off the desired vinyl carboxylates. The catalyst remains in the bottoms and can be reused if appropriate. Appropriately, the reaction and the workup, especially the purifying distillation, can be carried out in the presence of a polymerization inhibitor. The polymerization inhibitors used may, for example, be hydroquinone, hydroquinone monomethyl ether, 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, nitroso compounds such as isoacryloyi nitrate, nitrosodiphenylamine, N-nitrosocyclohexyl-hydroxyamine, methylene blue, phenothiazine, tannic acid or diphenylamine. The polymerization inhibitors are used generally in amounts of from 1 to 10 000 ppm, especially of from 100 to 1000 ppm, based in each case on the overall mixture.
The reaction proceeds selectively, i.e., even in the presence of other vinylatable groups in the compound of the formula II, such as OH or NH2, only the carboxyl groups are tinplated. If a compound of the formula II is used which, as well as the carboxyl group(s), also comprises another vinyl table group, the reaction temperature is appropriately selected within the range from 70 to 160°C and/or the reaction time within the range from 0.5 to 12 hours.
A preferred embodiment of the invention relates to the reaction of the compounds of the formula II in which R^ is H, Ci-Ce-alkyI, Cs-Cz-cycloalkyl or phenyl, where the alkyl group may be substituted as specified above under b) and the phenyl group as specified above under c), and n is 1 with acetylene.
A further preferred embodiment relates to the reaction of the compounds of the formula II in which R^ is CO2H and n is 1, or in which R^ is Ci-C2o-alkyl, especially Ci-C4-a!kyl, where R^ may be substituted as specified under b) above, and n is 2, with acetylene. Preference is given to carrying out this reaction at a temperature in the

range from 70 to 220°C, preferably from 130°C to 220°C, in particular from 140 to 180°C or from 150 to IZCC. Catalyst is used especially in an amount of from 0.00001 to 0.1 mol%, especially from 0.0001 to 0.01 mol%, based on equivalents of dicarboxylic acid. The reaction of adipic acid with acetylene is particularly preferred.
A further preferred embodiment relates to the reaction of the compounds of the formula II in which R^ is phenyl which may be substituted as defined under c) above, and n is 2, 3, 4, 5 or 6, especially 2 or 3, with acetylene. Preference is given to carrying out this reaction at a temperature in the range from 140 to 230°C, in particular from 150 to 200°C. The catalyst is used preferably in an amount of from 0.00001 to 0.1 mol%, especially from 0.0001 to 0.01 mol%, based on equivalents of polycarboxylic acid.
The present invention also provides compounds of the formula I

in which R^ is aryl and n is 2, 3, 4, 5 or 6, where aryl is optionally substituted by 1, 2 or 3 radicals which are each independently selected from Ci-C4-alkyl, halogen, Ci-C4-alkoxy, amino, mono-Ci-C4-alkylamino, di-Ci-C4-alkylamino, -OCOR^, -COOR^ -CONR^R^ -NR'COR^ -OCONR^R^ or -NR^COOR^ or Ri is Ca-Cy-cycloalkyI and n is 2 or 3, and R^ is H, d-Cs-alkyl, phenyl-Ci-C4-alkyl, phenyl which is optionally substituted by 1 or 2 Ci-C4-alkyl groups, or Cs-Cz-cycloalkyl.
Particular preference is given to the preparation of divinely phthalate, divinely terephthalate and divine isophthalate, and also of divinely cyclohexane-1,2, divinely cyclohexane-1,3 and divinely cyclohexane-1,4, vinyl pyridine-2-carboxylate, vinyl pyridine-3-carboxylate and vinyl pyridine-4-carboxylate, and also vinyl negotiate.
The present invention also provides the compounds of the formula I in which R^ is bicycloalkyi having from 6 to 9 carbon atoms or bicycloalkenyl having from 6 to 9 carbon atoms and one or two carbon-carbon double bonds and n is 1 or 2, or in which R^ is five- or six-mamboed heteroalkyi which has one or two heteroatoms which are each independently selected from N, O and S, where n is 1, 2 or 3; and R^ is H, Ci-Cs-alkyi, phenyl-Ci-C4-alkyi, phenyl which is optionally substituted by 1 or 2 Ci-C4-alkyi groups, or Ca-Cr-cycloalkyl.
The vinyl esters obtainable by the process according to the invention are suitable for use in materials which can be cured thermally or by energy-rich radiation. The

materials may be used as or in coating compositions, for example lacquers, printing inks or adhesives, as printing plates, as moldings, for producing photoresists, in stereolithography or as a casting material, for example for optical lenses. Substrates for the coating may, for example, be textile, leather, metal, plastic, glass, wood, paper or paperboard. The compounds of the formula I are usable as crosslinking agents in free-radical and cationic polymerizations. They are preferably used in UV-curable coatings, for example as reactive diluents.
The examples which follow illustrate the invention without restricting it. The GC analyses (GC: gas chromatography) were effected on a capillary column with a Carbowax (polyethylene glycol) film, for example DB Wax from J & W Scientific.
Examples
Example 1
A mixture of 36.0 g of benzoic acid (295 mom), 0.25 g of Re2(CO)io (0.38 moll) and
78.0 g of toluene were subjected to veneration at 140°C, a nitrogen pressure of 2 bar
and an acetylene pressure of 18 bar for 6 h. The yield determined by GC analysis was
99%.
Example 2
A mixture of 8.0 g of adipic acid (55 mmol), 0.10 g of Re(C0)5CI (0.28 mmol) and
17.3 g of toluene was subjected to vinylation at 140°C, a nitrogen pressure of 2 bar and
an acetylene pressure of 18 bar for 6 h. The yield determined by GC analysis was
96%.
Example 3
A mixture of 8.0 g of adipic acid (55 mmol), 0.10 g of Re(C0)5Br (0.25 mmol) and
17.3 g of toluene was subjected to vinylation at 140°C, a nitrogen pressure of 2 bar and
an acetylene pressure of 18 bar for 6 h. The yield determined by GC analysis was
95%.
Example 4
A mixture of 36.0 g of adipic acid (247 mmol), 0.10 g of Re2(CO)io (0.15 mmol) and
78.0 g of toluene were subjected to vinylation at 140°C, a nitrogen pressure of 2 bar
and an acetylene pressure of 18 bar for 6 h. The yield determined by GC analysis was
98%.
Example 5
A mixture of 300.0 g of adipic acid (2.045 mol), 1.00 g of Re2(CO)io (1.50 mmol) and
700.0 g of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar

and an acetylene pressure of 18 bar for 6 h. The disillusive workup of the reaction mixture in the presence of a polymerization inhibitor afforded the divines ester of the carboxylic acid in a yield of 87%.
Example 6
A mixture of 100.0 g of adipic acid (681.6 mol) and 0.50 of Re2(CO)io (0.75 mmol) was heated to 200°C without solvent for 2 h. After cooling to 160°C, the mixture was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h to obtain divinyl adipate.
Example 7
A mixture of 8.0 g of terephthalic acid (48 mmol), 0.10 g of Re2(CO)io (0.15 mmol) and 17.3 g of toluene was subjected to vinylation at 140°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. Divinyl terephthalate was obtained, which was detectable by means of GC-MS analysis.
Example 8
A mixture of 30.0 g (259 mmol) of fumaric acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 8 h. Divinyl fumarate was detected as the main product by means of GC-MS and GC analysis.
Example 9
A mixture of 30.0 g (181 mmol) of phthalic acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 12 h. Divinyl phthalate was detected as the main product by means of GC-MS and GC analysis.
Example 10
A mixture of 30.0 g (181 mmol) of isophthalic acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 20 h. Divinyl isophthalate was detected as the main product by means of GC-MS and GC analysis.
Example 11
A mixture of 30.0 g (197 mmol) of 4-methoxybenzoic acid, 0.5 g of Re2(CO)io
(0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen
pressure of 2 bar and an acetylene pressure of 18 bar for 18 h. Vinyl
4-methoxybenzoate was detected as the main product by means of GC-MS and GC
analysis.

Example 12
A mixture of 30.0 g (326 mmol) of pivalic acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 7 h. Vinyl pivalate was detected as the main product by means of GC-MS and GC analysis.
Example 13
A mixture of 30.0 g (348 mmol) of crotonic acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. Vinyl crotonate was detected as the main product by means of GC-MS and GC analysis.
Example 14
A mixture of 30.0 g (184 mmol) of 4-dimethylaminobenzoic acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. Vinyl 4-dimethylamino-benzoate was detected as the main product by means of GC-MS and GC analysis.
Example 15
A mixture of 30.0 g (192 mmol) of 4-chlorobenzoic acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 20 h. Vinyl 4-chloroben2oate was detected as the main product by means of GC-MS and GC analysis.
Example 16
A mixture of 30.0 g (417 mmol) of acrylic acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 140°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 17 h. Vinyl acrylate was detected as the main product by means of GC-MS and GC analysis.
Example 17
A mixture of 30.0 g (149 mmol) of 4-bromobenzoic acid, 0.5 g of Re2(CO)io
(0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen
pressure of 2 bar and an acetylene pressure of 18 bar for 4 h. Vinyl 4-bromobenzoate
was detected as the main product by means of GC-MS and GC analysis.
Example 18
A mixture of 30.0 g (348 mmol) of methacrylic acid, 0.5 g of Re2(CO)io (0.77 mmol) and

so ml of toluene was subjected to vinylation at 140°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 13 h. Vinyl methacrylate was detected as the main product by means of GC-MS and GC analysis.
Example 19
A mixture of 40.0 g (241 mmol) of terephthalic acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 175°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 2 h. Divinyl terephthalate was detected as the main product by means of GC-MS and GC analysis.
Example 20
A mixture of 40.0 g (345 mmol) of humanoid acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 1 h. Vinyl emanate was detected as the main product by means of GC-MS and GC analysis.
Example 21
A mixture of 40.0 g (313 mmol) of cyclohexanoic acid, 0.5 g of Re2(CO)io (0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 3.5 h. Vinyl cyclohexanoate was detected as the main product by means of GC-MS and GC analysis.
Example 22
A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re2(CO)io (0.12 mmol) and 100 ml of xylene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 24 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.
Example 23
A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re2(CO)io (0.12 mmol) and 100 ml of dioxane was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 2 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.
Example 24
A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re2(CO)io (0.12 mmol) and 100 ml of THF was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 1 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.

Example 25
A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re2(CO)io (0.12 mmol) and 100 ml of NMP was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 2.5 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.
Example 26
A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re2(CO)io (0.12 mmol) and 100 ml of diphenyl ether was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 2 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.
Example 27
A mixture of 6.5 g (253 mmol) of adipic acid, 0.08 g of Re2(CO)io (0.12 mmol) and 100 ml of decalin was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 10 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.
Example 28
A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re2(CO)io (0.12 mmol) and 100 ml of paraffin oil was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 12 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.
Example 29
A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re2(CO)io (0.12 mmol) and 100 ml of acetonitrile was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 12 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.
Example 30
A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re2(CO)io (0.12 mmol) and 100 ml of butyrolactone was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 26 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.
Example 31
A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re2(CO)io (0.12 mmol) and

100 ml of divinyl adipate was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 24 h. Divinyl adipate was detected as tlie main product by means of GC-MS and GC analysis.
Example 32
A mixture of 36.5 g (253 mmol) of adipic acid, 0.05 g of Re207 (1.03 mmol) and 90 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.
Example 33
A mixture of 8.0 g (56 mmol) of adipic acid, 0.10 g of rhenium powder (0.54 mmol) and
20 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and
an acetylene pressure of 18 bar for 6 h. Divinyl adipate was detected by means of GC
analysis.
Example 34
A mixture of 36.5 g (253 mmol) of adipic acid, 0.073 g of ReCb (0.25 mmol) and 100 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 30 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.
Example 35
A mixture of 36.5 g (253 mmol) of adipic acid, 0.062 g of ReCHsOs (0.25 mmol) and 100 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 30 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.
Example 36
A mixture of 36.5 g (253 mmol) of adipic acid, 5.0 g of Re207 on Si02/Al203 (3% Re, 0.8 mmol) and 100 ml of toluene was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 5 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.
Example 37
A mixture of 18.25 g (127 mmol) of adipic acid, 0.021 g of Re2(CO)io (0.03 mmol) and 60 ml of divinyl adipate was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 7 bar for 9.5 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.

Example 38
A mixture of 18.25 g (127 mmol) of adipic acid, 0.021 g of Re2(CO)io (0.03 mmol) and 60 ml of divinyl adipate was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 4 bar for 8 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.
Example 39
A mixture of 18.25 g (127 mmol) of adipic acid, 0.021 g of Re2(CO)io (0.03 mmol) and 60 ml of divinyl adipate was subjected to vinylation at 160°C, a nitrogen pressure of 1 bar and an acetylene pressure of 3 bar for 11 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.
Example 40
A mixture of 40.0 g (181 mmol) of cyclohexane-1,4-dicarboxylic acid, 0.05 g of Re2(CO)io (0.08 mmol) and 90 ml of dioxane was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 5 h. Divinyl cyclohexane-1,4-dicarboxylate was detected as the main product by means of GC-MS and GC analysis.
Example 41
A mixture of 8.0 g (55 mmol) of adipic acid, 1.33 g of Mn2(CO)io (3.4 mmol) and 20 ml
of dioxane was subjected to vinylation at 140°C, a nitrogen pressure of 2 bar and an
acetylene pressure of 18 bar for 6 h. Divinyl adipate was detected by means of GC
analysis.
Example 42
A mixture of 12.0 g (82 mmol) of adipic acid, 2.00 g of Mo(CO)6 (7.6 mmol) and 30 ml
of toluene was subjected to vinylation at 150°C, a nitrogen pressure of 2 bar and an
acetylene pressure of 18 bar for 6.5 h. Divinyl adipate was detected by means of GC
analysis.
Example 43
A mixture of 8.0 g (55 mmol) of adipic acid, 1.33 g of Fe(C0)5 (6.8 mmol) and 20 ml of
toluene was subjected to vinylation at 140°C, a nitrogen pressure of 2 bar and an
acetylene pressure of 18 bar for 6.0 h. Divinyl adipate was detected by means of GC
analysis.
Example 44

A' mixture of 40.0 g (171 mmol) of butanetetracarboxylic acid, 50 mg of Re2(CO)io (0.08 mmol) and 80 g of xylene (isomer mixture) was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 14.0 h. Tetravinyl butanetetracarboxylate was detected by means of MS analysis.
Example 45
A mixture of 10.0 g (55 mmol) of norbornenedicarboxylic acid, 50 mg of Re2(CO)io (0.08 mmol) and 80 g of xylene (isomer mixture) was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 4.0 h. Divinyi Norborne ate was detected by means of GC analysis.
Example 46
A mixture of 15.0 g (46 mmol) of 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic
acid (Het acid), 50 mg of Re2(CO)io (0.08 mmol) and 15 g of xylene (isomer mixture)
was subjected to vinylation at 160°C, a nitrogen pressure of 2 bar and an acetylene
pressure of 18 bar for 6.0 h. Het acid divinyi ester was detected by means of GC-MS
analysis.
Example 47
A mixture of 45.0 g (308 mmol) of adipic acid, 100 mg of Re2(CO)io (0.153 mmol) and 105 g of xylene (isomer mixture) was subjected to vinylation at 200°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 9 h. Divinyi adipate was detected as the main product by means of GC analysis.
Example 48
A mixture of 7.5 g (51 mmol) of adipic acid, of 100 mg of Re2(CO)io (0.153 mmol) and 142.5 g of xylene (isomer mixture) was subjected to vinylation at 240°C, a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 9 h. Divinyi adipate was detected as the main product by means of GC analysis.

What is claimed is:
1. A process for preparing vinyl carboxylate compounds of the formula I:

in which
a) R^ is H or -C00-CH=CH-R2 and n is 1,
b) R^ is Ci-C2o-alkyl, Ca-Cao-aikenyl or Cs-Cr-cycioaikyl, and n is 1, 2, 3 or 4, where R^ is optionally substituted by 1, 2 or 3 radicals which are each independently selected from phenyl, halogen, hydroxy, CrC4-alkoxy, amino, mono-Ci-C4-alkylamino, di-Ci-C4-alkylamino, -OCOR^ -COOR^, -CONR^R^ -NR^COR^ -OCONR^R^ or -NR^COOR^ or
c) R^ is aryl and n is 1, 2, 3, 4, 5 or 6, where aryl is optionally substituted by 1, 2 or 3 radicals which are each independently selected from Ci-C4-alkyl, halogen, hydroxy, Ci-C4-alkoxy, amino, mono-Ci-C4-alkylamino, di-Ci-C4-alkylamino, -OCOR^ -COOR^ -CONR*R^ -NR^COR^ -OCONR^R^ or -NR^COOR^ or
d) R^ is bicycloalkyi having from 7 to 9 carbon atoms or bicycloalkenyl having from 7 to 9 carbon atoms and one or two carbon-carbon double bonds, and n is 1 or 2, where the bicycloalkyi radical may be substituted by 1, 2, 3, 4, 5 or 6 radicals which are each independently selected from halogen or C1-C4-alkyl, or
e) R^ is five- or six-membered heterocyclyl which has one or two heteroatoms
which are each independently selected from N, O and S, and n is 1, 2 or 3,
where the heterocyclyl radical may be substituted by 1 or 2 radicals which
are each independently selected from halogen or Ci-C4-alkyl;
R^ is H, Ci-Cs-alkyI, phenyl-Ci-C4-alkyl, phenyl which is optionally substituted by 1 or 2 Ci-C4-alkyl groups, or Ca-Cj-cycloalkyl;
R^ is Ci-C4-alkyl;
R"* and R^, which may be the same or different, are each H or Ci-C4-alkyl;
comprising the reaction of a compound of the formula II

in which R^ is H, -COOH or as defined above under b) or c) and n is as defined above
with a compound of the formula III
H-C= C-R^ (III)
in which R^ is as defined above, in the presence of a catalyst which is selected from carbonyl complexes, oxides and halides of rhenium, of manganese, of tungsten, of molybdenum, of chromium and of iron and rhenium metal at a temperature of 2. The process according to claim 1, wherein the catalyst is selected from carbony complexes, oxides and halides of rhenium, of manganese and of molybdenum.
3. The process according to claim 2, wherein the catalyst used is Re2(CO)io.
4. The process according to any of the preceding claims, wherein the catalyst is used in an amount of from 0.000005 to 1 mor/o based on equivalents of the compound of the formula II.
5. The process according to any of the preceding claims, wherein the compound c the formula III is selected from acetylene, propyne, 1-butyne, 1-pentyne, 1-hexyne and phenylacetylene.
6. The process according to any of the preceding claims, wherein the compound c the formula II used is an aliphatic monocarboxylic acid.
7. The process according to claim 6, wherein the aliphatic monocarboxylic acid is selected from acetic acid, phenylacetic acid, propionic acid, alanine, butyric aci( hydroxybutyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, 2-methylpropionic acid, 2-methylbutyric acid, 3-methylbutyric acid, 2-methylpentanoic acid, 2-ethylhexanoic acid, 2-propyl-heptanoic acid, pivalic acid, 2,2-dimethylbutyric acid, 2,2-dimethylpentanoic acii 2,2-dimethylhexanoic acid, 2,2-dimethylheptanoic acid, 2,2-dimethyloctanoic acid, neononanoic acid, neodecanoic acid, neotridecanoic acid, stearic acid, ok acid, lauric acid, palmitic acid, cyclohexanecarboxylic acid, acrylic acid, methacrylic acid, crotonic acid and cinnamic acid.

8. The process according to any of claims 1 to 5, wherein the compound of the formula 11 used is an aliphatic polycarboxylic acid.
9. The process according to claim 8, wherein the aliphatic polycarboxylic acid is selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacicacid, agaric acid, 1,2,3-propanetricarboxylicacid, 1,2,3,4-butanetetra-carboxylic acid, cithc acid, malic acid, tartaric acid, glutamic acid, maleic acid and fumaric acid.
10. The process according to claim 9, wherein the compound of the formula II used is adipic acid.
11. The process according to any of claims 1 to 5, wherein the compound of the formula II used is a cycloaliphatic mono- or dicarboxylic acid.
12. The process according to claim 11, wherein the compound of the formula 11 used is cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,3-dicarboxyiic acid or cyclohexane-1,4-dicarboxylic acid.
13. The process according to any of claims 1 to 5, wherein the compound of the formula II used is a bicyclic or heterocyclic mono- or dicarboxylic acid.
14. The process according to claim 13, wherein the compound of the formula II used is a compound of the formula

15. The process according to claim 13, wlnerein ttie compound of the formula II used is 2-pyridinecarboxylic acid, 3-pyridinecarboxylic acid, 4-pyridinecarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, furan-2-carboxylic acid, furan-3-carboxylic acid, thiophene-2-carboxylic acid, thiophene-3-carboxylic acid or proline.
16. The process according to any of claims 8 to 15, wherein the reaction is carried out at a temperature in the range from 70 to 260°C.
17. The process according to any of claims 8 to 15, wherein the catalyst is used in an amount of from 0.000001 to 0.0025 mol%, based on equivalents of the compound of the formula II.
18. The process according to any of claims 1 to 5, wherein the compound of the formula II used is an aromatic monocarboxylic acid or an aromatic polycarboxylic acid.
19. The process according to claim 18, wherein the compound of the formula II used is benzoic acid, 2-, 3- or 4-methylbenzoic acid, salicylic acid, 2-, 3- or

4-aminoben2oic acid, 4-dimethylaminobenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetri-carboxyiic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,3,4-benzenetetracarboxylicacid, benzenepentacarboxylic acid or benzenehexacarboxyiic acid.
20. The process according to claim 18 or 19, wherein the reaction is carried out at a
temperature in the range from 140 to 230°C.
21. The process according to any of the preceding claims, where the compound of
the formula 111 is used in an excess of from 0.1 to 20 mol%, based on equivalents
of the compound of the formula II.
22. The process according to any of the preceding claims, wherein the compound of
the formula III used is acetylene.
23. A vinyl carboxylate of the formula 1

in which R"" is aryl and n is 2, 3, 4, 5 or 6, where aryl is optionally substituted by 1, 2 or 3 radicals which are each independently selected from Ci-C4-alkyl, halogen, Ci-C4-alkoxy, amino, mono- Ci-C4-alkylamino, di-Ci-C4-alkylamino, -OCOR^ -COOR^ -CONR*R^ -NR^COR^ -OCONR^R^ or -NR^COOR^, or in which Ri is Cs-Cz-cycloalky! and n is 2 or 3; and R^ is H, Ci-Cs-alkyI, phenyl-Ci-C4-alkyl, phenyl which is optionally substituted by 1 or 2 Ci-C4-alkyl groups, or C3-C7-cycloalkyl.
24. The vinyl carboxylate according to claim 22 of the formula I in which R^ is H.
25. The vinyl carboxylate according to claim 24, namely divinyl cyclohexane-
1,2-dicarboxylate, divinyl cyclohexane-1,3-dicarboxylate or divinyl cyclohexane-1,4-dicarboxylate.
26. The vinyl carboxylate according to claim 25, namely divinyl cyclohexane-
1,4-dicarboxylate.
27. Tetravinyl butane-1,2,3,4-tetracarboxylate.

■*
I
28. The vinyl carboxylate of the formula i:

in which R^ is bicycloalkyi having from 6 to 9 carbon atoms or bicydoalkenyl having from 6 to 9 carbon atoms and one or two carbon-carbon double bonds and n is 1 or 2, or in which R^ is five- or six-membered heterocyclyl which has one or two heteroatoms which are each independently selected from N, O and S, where n is 1, 2 or 3; and R^ is H, Ci-Ce-aikyl, phenyl-Ci-C4-alkyl, phenyl which is optionally substituted by 1 or 2 Ci-C4-alkyl groups, or Ca-Cr-cycloalkyl.
29. The use of the vinyl carboxylates according to any of claims 23 to 28 as
crosslinkers or reactive diluents.

Documents:

2558-CHENP-2008 EXAMINATION REPORT REPLY RECEIVED 28-09-2012.pdf

2558-CHENP-2008 FORM-3 28-09-2012.pdf

2558-CHENP-2008 CORRESPONDENCE OTHERS 22-03-2013.pdf

2558-CHENP-2008 EXAMINATION REPORT REPLY RECEIVED 21-08-2012.pdf

2558-CHENP-2008 FORM-3 22-03-2013.pdf

2558-CHENP-2008 OTHER PATENT DOCUMENT 21-08-2012.pdf

2558-CHENP-2008 AMENDED PAGES OF SPECIFICATION 21-08-2012.pdf

2558-CHENP-2008 AMENDED CLAIMS 21-08-2012.pdf

2558-CHENP-2008 AMENDED CLAIMS 22-03-2013.pdf

2558-CHENP-2008 CORRESPONDENCE OTHERS 10-07-2012.pdf

2558-CHENP-2008 FORM-3 21-08-2012.pdf

2558-CHENP-2008 POWER OF ATTORNEY 21-08-2012.pdf

2558-chenp-2008-abstract.pdf

2558-chenp-2008-claims.pdf

2558-chenp-2008-correspondence-others.pdf

2558-chenp-2008-description-complete.pdf

2558-chenp-2008-form-1.pdf

2558-chenp-2008-form-18.pdf

2558-chenp-2008-form-3.pdf

2558-chenp-2008-form-5.pdf

2558-chenp-2008-pct.pdf

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Patent Number

256506

Indian Patent Application Number

2558/CHENP/2008

PG Journal Number

26/2013

Publication Date

28-Jun-2013

Grant Date

26-Jun-2013

Date of Filing

23-May-2008

Name of Patentee

BASF SE

Applicant Address

67056, LUDWIGSHAFEN, GERMANY

Inventors:

#	Inventor's Name	Inventor's Address
1	KESSINGER, ROLAND	SOMMERGASSE 45/1, 69118 HEIDELBERG, GERMANY
2	STAFFEL, WOLFGANG	SOMMERGASSE ALTE SCHULSTRASSE 3, 69118 HEIDELBERG, GERMANY
3	HENKELMANN, JOCHEM	BASSERMANNSTRASSE 25, 68165 MANNHEIM, GERMANY

PCT International Classification Number

N/A

PCT International Application Number

N/A

PCT International Filing date

2006-11-22

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	102005055852.6	2005-11-23	Germany
2	102006046112.6	2006-09-28	Germany
3	102006027698.1	2006-06-14	Germany