DE102005055852A1 - Preparation of carboxylic acid vinyl compound, useful as cross-linking agent or reactive diluents, comprises reacting carboxylic acid compound with acetylene compound in the presence of catalyst e.g. carbonyl complex of rhenium - Google Patents

Abstract

Preparation of carboxylic acid vinyl compound (I) comprises reacting carboxylic acid compound (II) with acetylene compound (III), in the presence of a catalyst such as carbonyl complex of rhenium, manganese, tungsten, molybdenum, chrome or iron at =230[deg]C. Preparation of carboxylic acid vinyl compound (I) comprises reacting carboxylic acid compound (II) of formula (R 1>-(C(O)-OH) n) with acetylene compound (III) of formula (H-C?=C-R 2>), in the presence of a catalyst such as carbonyl complex of rhenium, manganese, tungsten, molybdenum, chromium or iron at =230[deg]C. R 1>H or -COO-CH=CH-R 2> (when n is 1), 1-20C-alkyl, 2-20C-alkenyl or 3-7C-cycloalkyl (optionally replaced by 1 or 2 of phenyl, halo or 1-4C-alkoxy) (when n is 1-3) or aryl (optionally substituted by 1-3 of 1-4C-alkyl, halo or 1-4C-alkoxy) (when n is 1-6); and R 2>H, 1-8C-alkyl, phenyl-1-4C-alkyl, phenyl (optionally substituted with 1-2 of 1-4C-alkyl) or 3-7C-cycloalkyl. In formula (II): R 1>1-20C-alkyl, 2-20C-alkenyl or 3-7C-cycloalkyl (optionally replaced by 1 or 2 of phenyl, halo or 1-4C-alkoxy) (when n is 1-3) or aryl (optionally substituted by 1-3 of 1-4C-alkyl, halo or 1-4C-alkoxy) (when n is 1-6), H or -COOH. An independent claim is included for a carboxylic acid vinyl ester compound (I). [Image].

Description

The The present invention relates to a process for the preparation of Carboxylic acid vinyl esters by Reaction of a carboxylic acid with an alkyne.

The addition of carboxylic acids to alkynes for the preparation of the corresponding carboxylic acid vinyl esters has long been known. In particular, zinc salts, such as the zinc salt of the carboxylic acid participating in the reaction, are used as suitable catalysts, see for example US 2,066,075 . US 8,455,998 and US 3,607,915 ,

Since the zinc salts have only low selectivity and stability, attempts were made to use other catalysts. That's how it describes US 5,430,179 the use of ruthenium complexes soluble in the reaction medium with a phosphine ligand. The EP 512 656 A describes a process for preparing vinyl derivatives of Bronsted acids such as carboxylic acids by reacting the Bronsted acid with an acetylenically unsaturated compound in the presence of a ruthenium catalyst supported on an inert porous support. In J. Org. Chem. 2004, 69, 5782-5784 describes the reaction of terminal alkynes with acetic acid or benzoic acid using Re (CO) ₅ Br as a catalyst. It has been found that, in particular in n-heptane and toluene as a solvent, the anti-Markovnikov adduct is obtained with high selectivity.

The The prior art method has in common that the yield on vinyl esters leaves something to be desired.

Of the The present invention is therefore based on the object, a method for the preparation of carboxylic acid vinyl esters to disposal to provide, which proceeds in high yield.

In addition, should the process can be carried out at temperatures at which also thermally labile carboxylic acids and carboxylic acid vinyl ester not decompose.

Finally, should the process can be carried out with small quantities of catalyst, around the cost of to limit the catalyst.

Surprisingly It has now been found that this task is solved when acting as a catalyst a carbonyl complex of rhenium, manganese, tungsten, molybdenum, chromium or iron.

worin

• a) R¹ für H oder -COO-CH=CH-R² und n für 1 stehen,
• b) R¹ für C₂-C₂₀-Alkyl, C₂-C₂₀-Alkenyl oder C₃-C₇-Cycloalkyl steht und n für 1, 2 oder 3 steht, wobei R¹ gegebenenfalls durch 1 oder 2 Reste substituiert ist, die unabhängig voneinander ausgewählt sind unter Phenyl, Halogen und C₁-C₄-Alkoxy, oder
• c) R¹ für Aryl und n für 1, 2, 3, 4, 5 oder 6 stehen, wobei Aryl gegebenenfalls durch 1, 2 oder 3 Reste substituiert sein kann, die unabhängig voneinander ausgewählt sind unter C₁-C₄-Alkyl, Halogen und C₁-C₄-Alkoxy;

R² für H, C₁-C₈-Alkyl, Phenyl-C₁-C₄-alkyl, Phenyl, das gegebenenfalls mit 1 oder 2 C₁-C₄-Alkylgruppen substituiert ist, oder C₃-C₇-Cycloalkyl steht;
durch Umsetzung einer Verbindung der Formel II

worin R¹ für H, -COOH oder die oben unter b) oder c) angegebenen Bedeutungen steht und n die oben angegebenen Bedeutungen besitzt,
mit einer Verbindung der Formel III H-C≡C-R2 (III)worin R² die oben angegebenen Bedeutungen besitzt, in Anwesenheit eines Katalysators, der ausgewählt ist unter Carbonylkomplexen des Rheniums, Mangans, Wolframs, Molybdäns, Chroms und Eisens bei einer Temperatur von ≤ 230°C umsetzt.The present invention therefore provides a process for the preparation of carboxylic acid vinyl esters of the formula I:

wherein

• a) R ^{1 is} H or -COO-CH = CH-R ² and n is 1,
• b) R ^{1 is} C ₂ -C ₂₀ -alkyl, C ₂ -C ₂₀ -alkenyl or C ₃ -C ₇ -cycloalkyl and n is 1, 2 or 3, where R ^{1 is} optionally substituted by 1 or 2 radicals independently selected from phenyl, halogen and C ₁ -C ₄ alkoxy, or
• c) R ^{1 is} aryl and n is 1, 2, 3, 4, 5 or 6, where aryl may optionally be substituted by 1, 2 or 3 radicals which are selected independently of one another from C ₁ -C ₄ -alkyl, Halogen and C ₁ -C ₄ alkoxy;

R ^{2 is} H, C ₁ -C ₈ alkyl, phenyl C ₁ -C ₄ alkyl, phenyl optionally substituted with 1 or 2 C ₁ -C ₄ alkyl groups, or C ₃ -C ₇ cycloalkyl ;
by reacting a compound of formula II

wherein R ^{1 is} H, -COOH or the meanings given above under b) or c) and n has the meanings given above,
with a compound of formula III HC≡CR 2 (III) wherein R ^{2 has} the meanings given above, in the presence of a catalyst which is selected from carbonyl complexes of rhenium, manganese, tungsten, molybdenum, chromium and iron at a temperature of ≤ 230 ° C.

at The alkyl groups may be straight-chain or branched alkyl groups with the specified carbon number. 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 C ₂ -C ₂₀ alkenyl groups are vinyl, 1- or 2-propenyl, butene-1-yl, buten-2-yl and isobutenyl.

halogen means fluorine, chlorine, bromine or iodine.

Examples of C ₃ -C ₇ -cycloalkyl groups are cyclopropyl, cyclobutyl, cycloheptyl and in particular cyclopentyl and cyclohexyl.

aryl is preferably phenyl or naphthyl.

When R ^{1 has} the meaning indicated above b), n is preferably 1 or 2.

When R ^{1 has} the abovementioned meaning c), n is preferably 1, 2 or 3.

The reaction is generally carried out in a homogeneous liquid phase, ie, a catalyst is used which is soluble in the reaction medium under the given reaction conditions or goes into solution during the reaction. The catalysts are preferably in the oxidation state 0 or I. The carbonyl complexes of rhenium or manganese, in particular in the mentioned oxidation states, have proved to be particularly suitable. Particularly effective are the carbonyl complexes of rhenium. One or more of the carbonyl groups may be replaced by suitable ligands such as halogens, especially chlorine or bromine, phosphine ligands such as triphenylphosphine, trimethylphosphine, triethylphosphine, tri-n-butylphosphine, etc., amine ligands such as NH ₃ , ethylenediamine, etc., alcohol ligands such as Phenol, methanol, ethanol, etc., or H ₂ O. Examples of suitable catalysts are Re ₂ (CO) ₁₀ , Re (CO) ₅ Cl, Re (CO) ₅ Br, ReBr (CO) ₃ (CH ₃ CN) _2, recp (CO) _3, Re (penta-methyl-Cp) (CO) _3, ReCl (CO) ₃ (CH ₃ CN) _2, ReBr (CO) ₃ (THF) _2, ReCl (CO) ₃ (THF ) ₂ , Mn ₂ (CO) ₁₀ , W (CO) ₆ , Mo (CO) ₆ , Cr (CO) ₆ and Fe (CO) ₅ . (Cp = cyclopentadiene; THF = tetrahydrofuran).

A particularly preferred catalyst is Re ₂ (CO) ₁₀ .

in the Generally, the catalyst is used in an amount of 0.000 005 to 1 mol%, preferably 0.000 005 to 0.5 mol%, more preferably 0.000 01 to 0.1 mol%, and especially 0.0005 to 0.05 mol%, 0.0001 to 0.05 mol%, 0.0005 to 0.01 mol% or 0.001 to 0.01 mol%, in each case based on equivalents the compound of formula II. The term "equivalents" as used herein refers to carboxyl groups of formula II which can react with the compound of formula III.

suitable Starting compounds of the formula II are aliphatic monocarboxylic acids. Examples for such carboxylic acids are formic, acetic, propionic, butyric, valeric, hexanoic, heptanoic, octanoic, nonanoic, decanoic, 2-methylpropionic, 2-methylbutyric, 3-methylbutyric, 2-methylpentanoic, 2-ethylhexanoic, 2-propylheptanoic, pivalic, neononanoic, neodecanoic , Neotridecanoic acid, stearic acid, oleic acid, lauric acid, palmitic acid, cyclohexanecarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid or Phenylacetic acid.

suitable Starting compounds of the formula II are also aliphatic polycarboxylic acid, in particular Dicarboxylic acids. examples for aliphatic polycarboxylic acids are oxalic acid, Malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, agaric acid, 1,2,3-propane tricarboxylic acid, maleic acid and fumaric acid, the use of adipic acid is particularly preferred.

suitable Starting compounds of the formula II are further aromatic monocarboxylic acids and Polycarboxylic acids. examples for Such carboxylic acids are benzoic acid, 2-, 3- or 4-methylbenzoic acid, phthalic acid, isophthalic or terephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,3,4-benzenetetracarboxylic acid, benzenepentacarboxylic acid and benzenecarboxylic acid.

suitable Starting compounds of the formula III are, for example, acetylene, Propyne, 1-butyne, 1-pentyne, 1-hexyne and phenylacetylene, with acetylene is particularly preferably used.

The ratio of compound of formula II to compound of formula III is in a wide range selectable. In general, however, one uses an excess of compound of Formula III, in particular a surplus from 0.1 to 20 mol%, based on the compound of formula II.

The Reaction is generally carried out in a suitable inert solvent carried out. If the compound of formula II at the temperature used liquid is, can also apply to a solvent be waived. Suitable inert solvents are aliphatic and aromatic hydrocarbons, such as pentane, hexane, heptane, toluene, Xylene, ethers, such as tetrahydrofuran or dioxane, chlorinated hydrocarbons, such as methylene chloride, 1,2-dichloroethane or chlorobenzene, acetonitrile, Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or polyethylene glycols or mixtures thereof.

The Reaction temperature is freely selectable over a wide range. she is generally chosen that rapid implementation takes place without leaving any starting compounds or decompose the product. In general, the temperature is in the range of 70 to 230 ° C, in particular 100 to 200 ° C, preferably 120 to 180 ° C, 130 to 170 ° C, 140 to 160 ° C and especially 140 to 150 ° C.

The reaction is usually carried out under pressure, preferably 1 to 30 bar (absolute), preferably 2 to 20 bar and especially 5 up to 25 bar or 10 to 20 bar. The pressure can be adjusted, for example, with the compound of the formula III used and / or an inert gas such as nitrogen.

Optionally, it is also possible to add reaction-promoting additives, such as zinc acetate, lithium salts, for example LiCl, Lewis acids, such as BF ₃ , etc., Lewis bases, such as triethylamine, pyridine, 1,5-diazabicyclo [4.3.0] non-5- en etc., substances that react with the catalyst at the CO and thereby can create free coordination sites, such as trimethylamino-N-oxide.

The Reaction can be batchwise, continuously or in a semi-batch process be performed. The work-up is done in the usual way Way, conveniently by distilling off the desired Carbonsäurevinylesters. The catalyst remains in the sump and can optionally be reused become. Conveniently, can the reaction and the work-up, in particular the purifying distillation, be carried out in the presence of a polymerization inhibitor. As polymerization inhibitors can for example, hydroquinone, hydroquinone monomethyl ether, 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, nitroso compounds such as isoacrylnitrate, Nitrosodiphenylamino of N-nitroso-cyclohexylhydroxylamine, methylene blue, Phenothiazine, tannic acid or diphenylamine can be used. The polymerization inhibitors are in amounts of 1 to 10,000 ppm, in particular from 100 to 1000 ppm, in each case based on the entire approach used.

A preferred embodiment of the invention relates to the reaction of the compounds of the formula II in which R ^{1 is} H, C ₁ -C ₆ -alkyl or phenyl and n is 1, with acetylene.

A further preferred embodiment relates to the reaction of the compounds of the formula II in which R ^{1 is} CO ₂ H and n is 1 or in which R ^{1 is} C ₁ -C ₂₀ -alkyl, in particular C ₁ -C ₄ -alkyl, and n is 2 stands, with acetylene. Preferably, this reaction is carried out at a temperature in the range of 70 to 180 ° C, in particular 100 to 170 ° C or 130 to 160 ° C. The catalyst is used in particular in an amount of 0.0001 to 0.1 mol%, in particular 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 formula II wherein R ¹ is phenyl and n is 2, 3, 4, 5 or 6, in particular 2 or 3, with acetylene. Vorugsweise this reaction is carried out at a temperature in the range of 140 to 230 ° C, in particular 150 to 200 ° C. The catalyst is preferably used in an amount of 0.0001 to 0.1 mol%, in particular 0.0001 to 0.01 mol%, based on equivalents of polycarboxylic acid.

worin R¹ für Aryl und n für 2, 3, 4, 5 oder 6 stehen, wobei Aryl gegebenenfalls durch 1, 2 oder 3 Reste substituiert sein kann, die unabhängig voneinander ausgewählt sein können unter C₁-C₄-Alkyl, Halogen und C₁-C₄-Alkoxy, und R² für C₁-C₈-Alkyl, Phenyl-C₁-C₄-alkyl, Phenyl, das gegebenenfalls mit 1 oder 2 C₁-C₄-Alkylgruppen substituiert ist, oder C₃-C₇-Cycloalkyl steht;
Besonders bevorzugt sind Phthalsäure-, Terephthalsäure- und Isophthalsäuredivinylester.The present compound also relates to the compounds of the formula I

wherein R ^{1 is} aryl and n is 2, 3, 4, 5 or 6, wherein aryl may optionally be substituted by 1, 2 or 3 radicals, which may be independently selected from C ₁ -C ₄ alkyl, halogen and C ₁ -C ₄ -alkoxy, and R ^{2 is} C ₁ -C ₈ -alkyl, phenyl-C ₁ -C ₄ -alkyl, phenyl which is optionally substituted by 1 or 2 C ₁ -C ₄ -alkyl groups, or C C ₃ -C ₇ cycloalkyl;
Particularly preferred are phthalic, terephthalic and divinyl isophthalates.

The according to the inventive method available Vinyl esters are suitable for use in masses which are thermal or can be cured by high-energy radiation. The crowds can as or in coating compositions, e.g. Paints, inks or adhesives, as printing plates, as shaped bodies, for the production of photoresists, in stereolithography or as casting compound, e.g. For optical lenses are used. Substrates for the coating can be, for example Textile, leather, metal, plastic, glass, wood, paper or cardboard be. The compounds of the formula I are included as crosslinking agents useful in free radical and cationic polymerizations. Preferably they are in UV-curable Paints, e.g. as a reactive diluent.

The explain the following examples the invention without limiting it. The GC analyzes (GC: gas chromatography) were carried out at a capillary column, with a carbowax (polyethylene glycol) film, e.g. DB Wax from J & W Scientific.

Examples

example 1

A mixture of 36.0 g of benzoic acid (295 mmol), 0.25 g of Re ₂ (CO) ₁₀ (0.38 mmol) and 78.0 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 99%.

Example 2

A mixture of 8.0 g adipic acid (55 mmol), 0.10 g Re (CO) ₅ Cl (0.28 mmol) and 17.3 g To Toluene was subjected to vinylation at 140 ° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 hours. The yield determined by GC analysis was 96%.

Example 3

A mixture of 8.0 g of adipic acid (55 mmol), 0.10 g Re (CO) ₅ Br (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 adipic acid (247 mmol), 0.10 g Re ₂ (CO) ₁₀ (0.15 mmol) and 78.0 g 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 98%.

Example 5

A mixture of 300.0 g of adipic acid (2.045 mol), 1.00 g of Re ₂ (CO) ₁₀ (1.50 mmol) and 700.0 g of toluene was subjected to vinylation at 160 ° C. under a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. Distillation of the reaction mixture in the presence of a polymerization inhibitor gave the divinyl ester of the carboxylic acid in a yield of 87%.

Example 6

A mixture of 100.0 g adipic acid (681.6 mol) and 0.50 Re ₂ (CO) ₁₀ (0.75 mmol) was heated without solvent to 200 ° C for 2 h. After cooling to 160 ° C wur de the mixture at 160 ° C a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h subjected to the vinylation to give the adipic acid divinyl ester was obtained.

Example 7

A mixture of 8.0 g of terephthalic acid (48 mmol), 0.10 g of Re ₂ (CO) ₁₀ (0.15 mmol) and 17.3 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. There was obtained the divinyl terephthalate, which could be detected by GCMS analysis.

Claims (22)

Process for the preparation of carboxylic acid vinyl compounds of the formula I:

in which a) R ^{1 is} H or -COO-CH = CH-R ² and n is 1, b) R ^{1 is} C ₁ -C ₂₀ -alkyl, C ₂ -C ₂₀ -alkenyl or C ₃ -C ₇ - Cycloalkyl and n is 1, 2 or 3, wherein R ^{1 is} optionally substituted by 1 or 2 radicals which are independently selected from phenyl, halogen and C ₁ -C ₄ alkoxy, or c) R ^{1 is} aryl and n is 1, 2, 3, 4, 5 or 6, wherein aryl may optionally be substituted by 1, 2 or 3 radicals which are independently selected from C ₁ -C ₄ alkyl, halogen and C ₁ -C ₄ alkoxy; R ^{2 is} H, C ₁ -C ₈ alkyl, phenyl C ₁ -C ₄ alkyl, phenyl optionally substituted with 1 or 2 C ₁ -C ₄ alkyl groups, or C ₃ -C ₇ cycloalkyl ; by reacting a compound of formula II

wherein R ^{1 is} H, -COOH or the meanings given above under b) or c) and n has the meanings given above, with a compound of formula III HC≡CR ² (III) wherein R ^{2 has} the meanings given above, in the presence of a catalyst which is selected from carbonyl complexes of rhenium, manganese, tungsten, molybdenum, chromium and iron at a temperature of ≤ 230 ° C. The method of claim 1, wherein the catalyst selected is among carbonyl complexes of rhenium and manganese. Process according to claim 2, wherein the catalyst used is Re ₂ (CO) ₁₀ . Method according to one of the preceding claims, wherein the amount of catalyst in an amount ranging from 0.000005 to 1 Mol%, based on equivalents the compound of formula II used. Method according to one of the preceding claims, wherein the compound of the formula III is selected from acetylene, propyne, 1-butyne, 1-pentyne, 1-hexyne, and phenylacetylene. Process according to claim 5, wherein as compound the formula III acetylene used. Method according to one of the preceding Claims, wherein the compound of the formula II used is an aliphatic carboxylic acid. The method of claim 7, wherein the aliphatic carboxylic acid selected is acetic, propionic, butyric, valeric, hexanoic, heptanoic, octanoic, nonanoic, decanoic, 2-methylpropionic, 2-methylbutyric, 3-methylbutyric, 2-methylpentanoic, 2-ethylhexanoic, 2-propylheptanoic, pivalic, neononanoic, neodecanoic, Neotridecanoic acid, stearic acid, oleic acid, lauric acid, palmitic acid, cyclohexanecarboxylic acid, acrylic acid, methacrylic acid and Crotonic. Method according to one of claims 1 to 6, wherein as Compound of formula II uses an aliphatic dicarboxylic acid. The method of claim 9, wherein the aliphatic dicarboxylic acid selected is under malonic acid, Succinic acid, glutaric, adipic acid, maleic and fumaric acid. Process according to claim 10, wherein as compound of the formula II adipic acid used. Method according to one of claims 9 to 12, wherein the Implementation is carried out at a temperature in the range of 70 to 200 ° C. A method according to any one of claims 9 to 13, wherein the Catalyst in an amount ranging from 0.000001 to 0.0025 mol%, based on equivalents the compound of formula II used. Method according to one of claims 9 to 13, wherein as Compound of formula III used acetylene. Method according to one of claims 1 to 6, wherein as Compound of formula II, an aromatic monocarboxylic acid or an aromatic polycarboxylic acid used. Process according to claim 15, wherein as compound Formula II benzoic acid, Phthalic acid, isophthalic acid or terephthalic acid used. A method according to claim 15 or 16, wherein the Implementation at a temperature in the range of 140 to 230 ° C performs. Method according to one of claims 15 to 17, wherein as Compound of formula III used acetylene. Method according to one of the preceding claims, wherein the compound of the formula III is present in an excess of from 0.1 to 20 mol%, based on equivalents the compound of formula II used. Carboxylic acid vinyl ester of the formula I

wherein R ^{1 is} aryl and n is 1, 2, 3, 4, 5 or 6, wherein aryl may optionally be substituted by 1, 2 or 3 radicals, which are independently selected from C ₁ -C ₄ alkyl, halogen and C ₁ -C ₄ alkoxy; and R ^{2 is} C ₁ -C ₈ alkyl, phenyl C ₁ -C ₄ alkyl, phenyl optionally substituted with 1 or 2 C ₁ -C ₄ alkyl groups, or C ₃ -C ₇ cycloalkyl. A carboxylic acid vinyl ester according to claim 20 of the formula I, wherein R ^{2 is} H. Use of the carboxylic acid vinyl esters according to claim 20 as a crosslinking agent or reactive diluent.