DE19927912A1 - Catalytic preparation of cyclic and/or polymer compounds by educt metathesis is performed in the presence of one or more heterogeneous catalysts and ionic liquids - Google Patents

Abstract

Cyclic and/or polymer compounds are prepared by metathesis of educts containing at least two functional groups in the form of optionally substituted alkene or alkyne units in the presence of one or more heterogeneous catalysts and ionic liquids. The catalysts are transition metal carbenes or transition metal compounds which form the carbenes under the conditions used, or transition metals salts in combination with an alkylation agent.

Description

The present invention relates to a method for producing cyclic and / or polymeric compounds by metathesis of starting materials that have at least two funk tional groups in the form of substituted or unsubstituted alkene or alkyne units included.

Metathesis is a mutual transalkylidation of alkenes and alkynes in the presence of catalysts. Reactions of this kind are used in a variety of technically important processes. An overview of this can be found in: M. Schuster, S. Blechert, Angew. Chem. 1997, 109, 2124 and S. Armstrong, J. Chem. Soc., Perkin Trans. 1, 1998, 371. Metathesis reactions include Oligomerization and polymerization of acyclic dienes (ADMET) and the Synthesis of carbocycles and heterocycles of different ring sizes by ring final metathesis (RCM, ring-closing metathesis). In addition, are crossed Metathesis of different alkenes known (Brümmer, O. et al. Chem. Eur. J. 1997, 3, 441).

Those for the metathesis reactions mentioned above can be found in WO-A-93/20111 ruthenium alkylidene compounds described by A. W. Stumpf, E. Saive, A. Deomceau and A.F. Noels in JJ Chem. Soc., Chem. Commun. 1995, 1127-1128 described ruthenium-based catalyst systems or those of P. Schwab, R. H. Grubbs and J. W. Ziller in J. Am. Chem. Soc. 1996, 118, 100 (see also WO 96/04289) described catalyst systems are used as catalysts.

More recently, the use of so-called non-aqueous ionic Liquids for metathesis reactions described.

Ionic liquids are salts or mixtures of salts, which are liquid in a wide temperature range. The advantage of ionic liquid nits is that they do not mix with aliphatic hydrocarbons.  

In organic reactions for which the use of a catalyst is necessary, can by adding ionic liquids and a suitable Kataly sator, which only or preferably dissolves in the ionic liquid, a heterogeneous Achieve catalysis.

US-A-5 104 840 describes the use of such mixtures as solvents for Transition metal complexes, especially nickel complexes that do not contain carbon-nickel Bindings included.

EP-B-448 445 describes the use of ionic liquids for dimerization of unsubstituted monoolefins using nickel chloride wrote. The disadvantage here is the use of organoaluminium halide, especially pyrophoric dichloroethyl aluminum, for the production of ionic liquid.

US-A-552 5567 describes the use of ionic liquids for the dispro Portioning of unsubstituted mono-olefins using tungsten catalysts. Again, an organoaluminium halide is mandatory before pulls the pyrophoric dichloroethyl aluminum, for the production of the ionic liquid used.

EP-A-882 691 describes the use of ionic liquids for dimerization tion of unsubstituted monoolefins using nickel chloride. In addition to the pyrophoric dichloroethyl aluminum also used here disadvantageous that the excess of the Lewis acid aluminum chloride in the ionic liquid an acid reaction mixture is formed.

The metathesis methods described above are only suitable for the Um setting of unsubstituted monoolefins, i.e. very simple organic moles cool. For the implementation of multiply substituted starting materials with functional ones These methods are not suitable for groups because, on the one hand, those described there  Catalysts are not applicable or because of their ionic liquids Composition or the fact that the reaction mixture is acidic in character has, are not suitable for other catalysts.

The object of the present invention was to provide a universally applicable method for the metathesis of starting materials which have at least two functional groups in the form of Contain alkene or alkyne units to provide that using ionic liquids is carried out. The procedure should also apply to substi tuated alkenes or alkynes can be used.

There has been a process for making cyclic and / or polymeric compound by metathesis of starting materials which contain at least two functional groups Contain the form of substituted or unsubstituted alkene or alkyne units, in the presence of one or more homogeneous or heterogeneous kata lysators found, which is characterized in that the metathesis in the presence is carried out by ionic liquids and that as catalysts transition metal carbenes or transition metal compounds that are under the reaction conditions form transition metal carbenes or transition metal salts in combination can be used with an alkylating agent.

Surprisingly, it was found that the presence of ionic liquid in metathesis reactions of starting materials that have at least two functional Groups in the form of substituted or unsubstituted alkene or alkyne units contain leads to the fact that the service life of the catalyst is extended because it in the ionic liquid can be used for further metathesis reactions.

In a preferred embodiment, the present invention relates to the provision of carbocyclic or heterocyclic compounds with ring sizes ≧ 5 ring members, including the medium (8 to 11 ring links) and large (≧ 12 ring links) Rings and / or the preparation of polymeric compounds, which are Homopolymers, copolymers or block copolymers can act.  

In ring closure metathesis reactions, the ring closure reaction is in competition with Polymerization. If this reaction is carried out with starting materials which have at least two contain functional groups in the form of alkene or alkyne units, so ent are mixtures of cyclic compounds and polymers.

The formation of cyclic compounds is accomplished by performing the Reaction in organic solvents at high dilution or through the The addition of larger volumes of ionic liquids favors. This applies in particular for the production of medium (8 to 11 ring links) and large (≧ 12 ring limbs) wrestling.

The large ones required to achieve the necessary high dilution Reaction volumes of organic solvents limit the maximum Space / time yields. The separation of the products after the reaction has ended requires time-consuming separation operations such as chromatography and mostly leads to irreversible deactivation of the catalyst used.

By using larger volumes of ionic liquids, however, remove the desired products easily, as they are in the organic Are phase that is immiscible with the ionic liquid. You choose a catalyst that is exclusively or preferably in the ionic liquid dissolves, the deactivation of the catalyst can be ver after working up avoid and the phase that contains the ionic liquid and the catalyst be used for further metathesis reactions.

Educts are preferably used in the process according to the invention which, in addition to at least one of the functional groups involved in the metathesis reaction further substituents which are inert in the metathesis reaction and / or a Heteroatom included. These substituents or heteroatoms can be independent are selected from: branched or unbranched alkyl radicals, aromatic  or non-aromatic carbocyclic rings, carboxylic acids, esters, ethers, epoxides, Silyl ethers, thioethers, thioacetals, anhydrides, imines, silylenol ethers, Ammonium salts, amides, nitriles, perfluoroalkyl groups, mixed dialkyl groups, Alkynes, alkenes, halogens, alcohols, ketones, aldehydes, carbamates, carbonates, Urethanes, sulfonates, sulfones, sulfonamides, nitro groups, organosilane units, Metal centers, oxygen, nitrogen, sulfur, phosphorus-containing heterocycles.

For the process according to the invention, α, ω- Dienes used which are at least one other, are inert in the metathesis reaction may contain behavioral substituents and / or a heteroatom. This sub stituents or heteroatoms can be chosen independently from ver branched or unbranched alkyl radicals, aromatic or non-aromatic carbo cyclic rings, carboxylic acids, esters, ethers, epoxies, silyl ethers, thioethers, thio acetals, anhydrides, imines, silyl enol ethers, ammonium salts, amides, nitriles, per fluoroalkyl groups, mixed dialkyl groups, alkynes, alkenes, halogens, alcohols, Ketones, aldehydes, carbamates, carbonates, urethanes, sulfonates, sulfones, sulfones amides, nitro groups, organosilane units, metal centers, oxygen, nitrogen, Heterocycles containing sulfur and phosphorus.

In particular, α, ω-dienes which carry a substituent NRR ¹ in the oc position to a double bond are used for the process according to the invention, where
R is an organic substituent, preferably hydrogen, optionally fused aryl, alkyl, CN, COOR2 or halogen,
R ^{1 is} tert-butyl, P (R) ₂ , P (R ² ) ₂ , COR, SO ₂ PhR, COOR or CONRR ² ,
R ^{2 is} alkyl or phenyl,
R and R ¹ together

mean and said α, ω-dienes also at any other position in the molecule, with the exception of the α- Position, can carry at least one further substituent R.

When using these dienes as starting materials for the process according to the invention, cyclic and / or polymeric compounds are available which bear a substituent NRR ¹ in the α-position to the double bond, where R and R ^{1 have} the meaning given above.

In a particularly preferred embodiment, the above-mentioned α, ω-dienes are compounds of the general formula (I)

in which R, R ¹ and R ^{2 have} the meaning given above and
n denotes the number 1, 2, 3 or 4, preferably 1 or 2, particularly preferably 1.

When compounds of the general formula (I) are used, the process according to the invention preferably uses cyclic compounds of the general formula (II)

in which R, R ¹ , R ² and n have the meaning given above and the double bond can also be substituted by at least one radical R, and also polymer products.

Educts are very particularly preferred for the process according to the invention Diallylamine or 3-amino-1,7-ocdiene, particularly preferred in their N-carboxy methyl-protected form or I, 7-octadiene, 10-undecenoyl allylamide, 1,4-bis-oxy propen-2-yl-butin-2 or 10-undecenoic acid-buten-4-yl ester used.

Mixtures of starting materials can also be used in the process according to the invention become. The starting materials can be added to the reaction medium as a mixture are or added to the reaction medium sequentially.

For the process according to the invention are used as catalysts or catalyst precursors transition metal carbenes or transition metal compounds that are among the Reaction conditions form transition metal carbenes or transition metal salts in Compound used with an alkylating agent, these catalysts can be both ionic and non-ionic.

For the process according to the invention, preference is given to using catalysts of the general formulas (III) to (VI), where M denotes ruthenium or osmium, preferably ruthenium.

R ³ to R ⁷ are independently selectable radicals from hydrogen, C ₁ -C ₂₀ alkyl, C ₃ -C ₈ cycloalkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₆ -C ₁₈ aryl, C ₁ -C ₂₀ carboxylate, C ₁ -C ₂₀ alkoxy, C ₂ -C ₂₀ alkenyloxy, C ₂ -C ₂₀ alkynyloxy, C ₆ -C ₁₈ aryloxy, C ₂ -C ₂₀ alkoxycarbonyl, C ₁ -C ₂₀ alkylthio, C ₁ - C ₂₀ alkylsulfonyl or C ₁ -C ₂₀ alkylsulfinyl, N-aryl; each optionally substituted with C ₁ -C ₁₂ alkyl, perfluoroalkyl, halogen, C ₁ -C ₅ alkoxy or C ₆ -C ₁₈ aryl. The radicals R ³ to R ⁷ can be linked to one another in cyclic compounds.

X ¹ to X ³ are independently selectable anionic ligands, in particular F ^- , Cl ^- _, Br ^- , CN ^- , SCN ^- , R ³ O ^- , R ³ R ⁴ N ^-, (R ³ -R ⁷ ) -allyl ^- , (R ³ -R ⁷ ) -Cyclopenta dienyl ^- , where the radicals R ³ to R ⁷ meet the definition already mentioned.

L ¹ to L ³ are independently selectable neutral ligands, in particular CO, CO ₂ , R ³ NCO, R ³ R ⁴ C = CR ⁵ R ⁶ , R ³ C∼CR ⁴ , R ³ R ⁴ C = NR ⁵ , R ³ C∼N, R ³ OR ⁴ , R ³ SR ⁴ , NR ³ R ⁴ R ⁵ , PR ³ R ⁴ R ⁵ , AsR ³ R ⁴ R ⁵ , SbR ³ R ⁴ R ⁵ , the radicals R ³ to R ⁵ meet the definition already mentioned.

m is 1 or 2.  

Particularly preferred catalysts or catalyst precursors are compounds of the general formulas (III) and (IV) with L ¹ and L ² = PR ³ R ⁴ R ⁵ , where R ³ to R ⁵ correspond to the definitions given above, very particularly preferred radicals being aryl or alkyl, especially secondary alkyl radicals or cycloalkyl radicals.

The following compounds are very particularly preferably used as catalysts for the process according to the invention:

where Cy = cyclohexyl, iPr = isopropyl, Ph = phenyl.

The catalysts can be used in isolated form or in situ in the reaction medium are generated from catalyst precursors. The amounts of catalyst required for the method used according to the invention are generally from 0.001 to 15 mol%, based on the starting materials. The method according to the invention is preferred with 0.1 to 12 mol% of catalyst, particularly preferably based on 0.5 to 9 mol% on the starting materials.  

The ionic liquids used for the process according to the invention are Salts or salt mixtures in a temperature range from -20 ° C to 300 ° C are liquid.

Ionic liquids are preferred for the process according to the invention set, the aluminum halides in combination with at least one quaternary Ammonium halide and / or at least one quaternary phosphonium halide contain.

Heterocyclic quaternary ammonium compounds are particularly preferred Compounds containing at least one nitrogen atom are used. these are for example pyridinium compounds or imidazolium compounds.

Aluminum chloride in are very particularly preferred as ionic liquids Combination with 1-methyl-3-butylimidazolium chloride, 1-methyl-3-ethylimidazo lium chloride, N-butylpyridinium chloride and / or tetrabutylphosphonium chloride ver turns.

Ionic liquids are preferably used for the process according to the invention uses a combination of aluminum halide and quaternary ammo nium halides and / or quaternary phosphonium halides in a molar ratio nis (0.6-1): 1 exist. The molar ratio of aluminum halide to quar tary ammonium halide and / or quaternary phosphonium halide should never be greater than 1, otherwise an excess of Lewis acid in the reaction mixture is present. This acidic reaction mixture leads to a deactivation of the over gear metal carbene catalysts.

Ionic liquids are also preferred for the process according to the invention the ammonium hexafluorophosphate, ammonium tetrafluoroborate, Contain ammonium tosylate, or ammonium hydrogen sulfate or from ammonium  hexafluorophosphate, ammonium tetrafluoroborate, ammonium tosylate or ammo nium bisulfate exist.

Pyridinium hexafluoro are particularly preferred as ionic liquids phosphate, 1-methyl-3-butylhexafluorophosphate, pyridinium tetrafluoroborate, pyridi nium bisulfate or N-butylpyridinium hexafluorophosphate used.

Kombina can also be used as ionic liquids in the process according to the invention ions of aluminum halide with mixtures of quaternary ammonium halo genides and / or quaternary phosphonium halides and mixtures of Ammonium hexafluorophosphates, ammonium tetrafluoroborates, ammonium tosy laten or ammonium bisulfates are used.

The process according to the invention can be carried out in the presence of one or more Additives, preferably a solvent, are carried out, for example show an easier separation of the products from the ionic liquid and the catalyst located therein is possible. In the presence of an additive and the ionic liquids result in a heterogeneous catalytic system if ionic catalysts or catalysts that are preferred in the ionic Dissolve liquid, be used. After the metathesis reaction has ended the ionic phase that contains the catalyst simply from the additive with the one in it reaction product located can be separated. The catalyst in the ionic Liquid can be used for further metathesis reactions without intermediate cleaning steps be used.

Such additives can be selected, for example, from: phosphorus compounds, Amines, perfluorinated compounds, metal alkoxides and organic solvents. Halogenated carbons are particularly suitable as organic solvents Hydrogen such as dichloromethane, trichloromethane, carbon tetrachloride, 1,2 dichloroethane, trichloroethane, aromatic compounds such as Benzene, toluene, xylene, cumene, halobenzenes, alkanes such as pentane,  Hexane, cyclohexane, esters such as tert-butyl methyl ester or acetoacetic acid esters, ethers such as diethyl ether, tetrahydrofuran, dimethoxyethane, Amides such as dimethylformamide, antioxidants such as Hydroquinones, acetone, dimethyl carbonate or alcohols.

C ₅ -C ₂₀ -Alkanes, ethers or halogenated carbons are preferably used as additives for the process according to the invention.

In the process according to the invention, pentane, n- Hexane, methyl tert-butyl ether or dichloromethane used.

The process according to the invention is preferred at pressures in the range from 0.1 to 10 bar carried out, particularly preferably at atmospheric pressure. The invention however, the appropriate method can also be used for negative pressures up to 0.01 bar and positive pressures up to 100 bar.

The method according to the invention is usually in a temperature range from -20 ° C to 200 ° C, preferably from 0 ° C to 150 ° C, very particularly preferably from 20 ° C to 100 ° C.

The cyclic compounds which can be prepared by the process according to the invention or polymers can be further cleaned and processed using standard methods become. The catalyst in the ionic liquid can be cleaned without intermediate steps can be used for further metathesis reactions.  

Examples

The examples below describe metathesis reactions in Presence of ionic liquids (and additives) under preferred conditions gung. However, they are in no way intended to limit the scope of the present invention restrict. The abbreviation Cy stands for Cyclohexyl, Ph for Phenyl, iPr for Isopropyl and TfO for triflate.

example 1

Preparation of N-carboxymethyl-2,5-dihydropyrrole

155 mg (1 mmol) N-carboxymethyl-diallylamine and 17 mg (tricyclohexyl phosphine) benzylidene-chloro-ruthenium (IV) -2 - [(2,6-iisopropylphenyl) imino] methyl- 4-nitrophenolate (2 mol%) were dissolved in a liquid mixture of 579 mg 1- Methyl 3-ethylimidazolium chloride (4 mmol) and 533 mg aluminum trichloride (4 mmol) dissolved under an argon atmosphere. The mixture was washed with 3 ml of absolute n- Hexane overlaid. The mixture was allowed to react at room temperature with stirring for 30 minutes. After phase separation, the ionic phase was ge three more times with n-hexane to wash. A gas chromatographic examination of the organic phase showed a product share of 30% with respect to N-carboxymethyl-2,5-dihydropyrrole. A he covering the catalyst phase again with a solution of 155 mg (1 mmol) N-carboxymethyl-diallylamine in 3 ml of n-hexane, reaction time again 30 minutes  and an analogous work-up gave a yield of 20% with respect to N- Carboxymethyl-2,5-dihydropyrrole.

Example 2

Preparation of N-carboxymethyl-3,4,5,6-tetrahydroaniline

92 mg (0.5 mmol) of N-carboxymethyl-3-amino-1,7-octadiene and 4 mg of bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride (1 mol%) were in a heated Schlenk tube under an argon atmosphere in a liquid Mixture of 586 mg 1-methyl-3-ethylimidazolium chloride (4 mmol) and 533 mg aluminum trichloride (4 mmol) dissolved. The mixture was allowed to react at 50 ° C for two hours. After aqueous work-up, the mixture was filtered through a very short column of silica gel (0.5 cm), washed four times with 1 ml each of acetonitrile and concentrated.
Yield: 77 mg of N-carboxymethyl-3,4,5,6-tetrahydroaniline (0.49 mmol, 99% of theory).
¹ H NMR (400 MHz, CDCl ₃ ) δ 5.85 (1H, d, J = 9.0 Hz), 5.60 (1H, d, J = 9.0 Hz), 4.70 (1H, s), 4.20 (1H, s), 3.65 (3H, s), 1.98 (2H, m), 1.90 (1H, m), 1.62 (2H, m), 1.52 (1H, m).

Example 3

Preparation of N-carboxymethyl-3,4,5,6-tetrahydroaniline

92 mg (0.5 mmol) of N-carboxymethyl-3-amino-1,7-octadiene and 10 mg of the ruthenium catalyst (tricyclohexylphosphine) benzylidene-chloro-ruthenium- (IV) -2 - [(2.6 -diisopropylphenyl) imino] methyl-4-nitro phenolate were in a heated Schienk tube under an argon atmosphere in 1 ml of abs. Hexane and a mixture of 290 mg (2 mmol) of 1-methyl-3-ethylimidazolium chloride and 266 mg (2 mmol) of aluminum trichloride. The mixture was allowed to react at 50 ° C. for 3 hours. For working up, the organic phase was pipetted off and the phase of the ionic liquids was washed twice with 2 ml of hexane each time. The combined hexane phases were concentrated. Finally, the mixture was filtered through a very short silica gel column (0.2 cm), washed once with 1 ml of acetonitrile and concentrated. The catalyst dissolved in the ionic liquid is available for further reaction with substrate in hexane.
Yield: 74 mg of N-carboxymethyl-3,4,5,6-tetrahydroaniline (0.48 mmol, 96% of theory).

Example 4

Preparation of N-carboxymethyl-3,4,5,6-tetrahydroaniline

92 mg (0.5 mmol) N-carboxymethyl-3-amino-1,7-octadiene and 4 mg bis (tricyclo hexylphosphine) benzylidene ruthenium (IV) dichloride (1 mol%) were used in one heated Schienkrohr under an argon atmosphere in a liquid mixture of 684 mg N-butylpyridinium chloride (4 mmol) and 533 mg aluminum trichloride (4 mmol) solved. The mixture was allowed to react at 50 ° C for two hours. After aqueous work-up was filtered through a very short silica gel column (0.5 cm), four times with 1 ml each Washed acetonitrile and concentrated.

Yield: 77 mg of N-carboxymethyl-3,4,5,6-tetrahydroaniline (0.49 mmol, 98% of the Theory).

Example 5

Manufacture of tetrahydrobenzene

110 mg (1 mmol) 1,7-octadiene and 17 mg (tricyclohexylphosphine) -benzylidene- chloro-ruthenium- (IV) -2 - [(2,6-diisopropylphenyl) imino] methyl-4-nitro-phenolate (2 mol%) were in a heated Schlenk tube under an argon atmosphere in 3 ml absolute pentane dissolved. A liquid mixture of 579 mg of 1-methyl-3- ethylimidazolium chloride (4 mmol) and 533 mg aluminum trichloride (4 mmol) added. The mixture was allowed to react at room temperature for 30 minutes. For Working up, the organic phase was pipetted off and the ionic phase Liquids washed two more times with 2 ml each of pentane. The United Pentane phases were concentrated. In conclusion, it was a very short Filtered silica gel (0.2 cm), washed once with 1 ml of pentane and constricted.

The yield of tetrahydrobenzene was determined by gas chromatography (internal standard: tetradecane) and was 99% of theory.

After covering the reaction solution again with a mixture of 110 mg (1 mmol) 1,7-octadiene in pentane, a reaction time of 30 minutes and on closing phase separation gave a yield of 63% tetrahydrobenzene.

Example 6

Manufacture of tetrahydrobenzene

28 mg of 1,7-octadiene (0.25 mmol) were placed in a 20 ml Schlenkohr in a mixture of 345 mg (2 mmol) of 1-methyl-3-butylimidazo  lium chloride and 266 mg (2 mmol) aluminum trichloride dissolved. 11 mg of the cationic catalyst described in the reaction scheme above (5 mol%). The reaction solution was over with 3 ml of methyl tert-butyl ether layers. The mixture was allowed to react at a temperature of 40 ° C. for 90 minutes and separated then the organic phase. The ionic phase was triple with methyl extracted tert-butyl ether.

The desired tetrahydro was found to be 32% by gas chromatography determined benzene. This result was in a subsequent second metathesis reaction achieved again using the same ionic phase.

Example 7

Preparation of aminocyclotridec-11-en-2-one

58 mg (0.25 mmol) 10-undecenoyl allylamide and 10 mg (tricyclohexylphosphine) - benzylidene-chloro-ruthenium- (IV) -2 - [(2,6-diisopropylphenyl) imino] methyl-4-nitro Phenolate (5 mol%) was dissolved in 3 g of 1-methyl-3-butylimidazolium hexafluorophosphate solved. The mixture was allowed to react at 40 ° C. for 14 h. The ionic phase was with dichlor extracted methane. After filtration through a very short silica gel column (length approx. 0.5 cm), about 80% of the desired product was obtained (yield determination by means of gas chromatography). The E / Z ratio is about 5: 1.  

Example 8

Metathesis of buten-4-yl 10-undecenate

238 mg buten-4-yl 10-undecenate and 8 mg (tricyclohexylphosphine) benzene cylidene-chloro-ruthenium- (IV) -2 - [(2,6-diisopropylphenyl) imino] methyl-4-nitro phenolate (8 mol%) were mixed in a mixture of 580 mg (4 mmol) 1-methyl-3- ethylimidazolium chloride and 533 mg aluminum trichloride (4 mmol) dissolved. The Mixture was overlaid with 40 ml of absolute pentane. One left under good Mix thoroughly over a period of five hours at room temperature yaw. In addition to a large percentage of polymer, approx. 10% dimers of the received service.

Example 9

Preparation of 3,3'-bis-2,5-dihydrofuranyl

166 mg of 1,4-bis-oxypropen-2-yl-butyn-2 were mixed with 41 mg (tricyclohexylphosphine) - benzylidene-chloro-ruthenium- (IV) -2 - [(2,6-diisopropylphenyl) imino] methyl-4 -nitro phenolate (5 mol%) in a heated Schienk tube under an argon atmosphere in a liquid mixture of 2.31 g of 1-methyl-3-ethylimidazolium chloride (16 mmol) and 2.13 g of aluminum trichloride (16 mmol). The mixture was allowed to react at 40 ° C for 18 hours. For working up, the ionic phase was washed several times with toluene. The combined toluene extracts were filtered through a very short silica gel column (0.5 cm). It was washed four times with 10 ml of toluene and concentrated.
Yield: 120 mg of 3,3'-bis-2,5-dihydrofuranyl (87% of theory).

Example 10

Preparation of 1,3-di (3-trimethylsilylpropen-1-yl) -cyclopentane and 1- (3-trimethylsilyl-propen-1-yl) -3-vinyl-cyclopentane

47 mg norbornene (0.5 mmol) and 126 mg allyltrimethylsilylsilane (1.1 mmol) were made in a mixture of 289 mg (2 mmol) of 1-methyl 3-ethylimidazolium chloride and 266 mg (2 mmol) aluminum trichloride dissolved. On finally 10 mg (3 mol%) of the above-mentioned molybdenum catalyst were added given this reaction mixture. This mixture was covered with 3 ml of n- Hexane and allowed to react for one hour at room temperature.  

After separating the organic phase and extracting the ionic phase with n- Hexane and after combining the organic extracts became gaschro examined matographically. Yield of disilylated product 1,3-di (3-trimethylsilyl propen-1-yl) -cyclopentane: approx. 60% of theory, yield of monosilylated pro product 1- (3-trimethylsilyl-propenl-yl) -3-vinyl-cyclopentane: approx. 20% of theory. There In addition, polymeric products are found. No more educt can be added be shown.

Claims (16)

1. A process for the preparation of cyclic and / or polymeric compounds by metathesis of starting materials which contain at least two functional groups in the form of substituted or unsubstituted alkene or alkyne units, in the presence of one or more homogeneously or heterogeneously present catalysts, characterized in that the Metathesis is carried out in the presence of ionic liquids and that as catalysts, transition metal carbenes or transition metal compounds which form transition metal carbenes under the reaction conditions or transition metal salts are used in conjunction with an alkylating agent. 2. The method according to claim 1, characterized in that it is in the polymeric compounds around homopolymers, copolymers or block co polymeric. 3. The method according to claim 1, characterized in that it is in the cyclic compounds with carbocyclic or heterocyclic compounds Ring sizes ≧ 5 ring members. 4. The method according to one or more of the preceding claims 1 to 3, characterized in that the starting materials in addition to those at the metathesis tion involved functional groups at least one other, in the Metathesis reaction inertly acting substituents and / or a heteroatom contain. 5. The method according to claim 4, characterized in that said sub substituents or heteroatoms can be selected independently from: branched or unbranched alkyl radicals, aromatic or non-aromatic carbo cyclic rings, carboxylic acids, esters, ethers, epoxies, silyl ethers, thioethers,  Thioacetals, anhydrides, imines, silyl enol ethers, ammonium salts, amides, Nitriles, perfluoroalkyl groups, mixed dialkyl groups, alkynes, alkenes, halo genes, alcohols, ketones, aldehydes, carbamates, carbonates, urethanes, sulfo nates, sulfones, sulfonamides, nitro groups, organosilane units, metal centers, oxygen, nitrogen, sulfur, phosphorus-containing heterocycles. 6. The method according to claim 5, characterized in that as starting materials α, ω- Dienes are used that have at least one other, in the meta theses reaction inert inert substituents and / or a heteroatom can contain. These substituents or heteroatoms can be independent dependent are chosen from branched or unbranched alkyl residues, aroma table or non-aromatic carbocyclic rings, carboxylic acids, esters, Ethers, epoxides, silyl ethers, thioethers, thioacetals, anhydrides, imines, Silyl enol ethers, ammonium salts, amides, nitriles, perfluoroalkyl groups, mixed dialkyl groups, alkynes, alkenes, halogens, alcohols, ketones, Aldehydes, carbamates, carbonates, urethanes, sulfonates, sulfones, sulfonamides, Nitro groups, organosilane units, metal centers, oxygen, nitrogen, Heterocycles containing sulfur and phosphorus. 7. The method according to claim 6, characterized in that α, ω-dienes which bear a substituent NRR ¹ in the α-position to a double bond, a
R is an organic substituent, preferably hydrogen, optionally fused aryl, alkyl, CN, COOR ² or halogen,
R ^{1 is} tert-butyl, P (R) ₂ , P (R ² ) ₂ , COR, SO ₂ PhR, COOR or CONRR ² ,
R ^{2 is} alkyl or phenyl,
R and R ¹ together
mean
and said α, ω-dienes can also carry at least one further substituent R at any other position in the molecule, with the exception of the α position. 8. The method according to claim 7, characterized in that α, ω-dienes of the general formula (I) are used
in which R, R ¹ and R ^{2 have} the meaning given in claim 7 and n denotes the number 1, 2, 3 or 4, preferably 1 or 2, particularly preferably 1. 9. The method according to claim 7, characterized in that as α, ω-dienes Diallylamine or 3-amino-1,7-octadiene, particularly preferably in their N- Carboxymethyl-protected form or 1,7-octadiene, 10-undecenoyl-allyl amide, 1,4-bis-oxypropen-2-yl-butyn-2 or 10-undecenoic acid-buten-4-yl ester be used. 10. The method according to one or more of the preceding claims 1 to 9, characterized in that compounds of the general formula (III) to (VI) can be used as catalysts, where M is ruthenium or osmium
and
R ³ to R ⁷ independently selectable radicals are from: hydrogen, C ₁ -C ₂₀ alkyl, C ₃ -C ₈ cycloalkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₆ -C ₁₈ aryl, C ₁ -C ₂₀ carboxylate, C ₁ -C ₂₀ alkoxy, C ₂ -C ₂₀ alkenyloxy, C ₂ -C ₂₀ alkynyloxy, C ₆ -C ₁₈ aryloxy, C ₂ -C ₂₀ alkoxycarbonyl, C ₁ -C ₂₀ alkylthio, C ₁ -C ₂₀ alkylsulfonyl or C ₁ -C ₂₀ alkylsulfinyl, N-aryl; each optionally substituted with C ₁ -C ₁₂ alkyl, perfluoroalkyl, halogen, C ₁ -C ₅ alkoxy or C ₆ -C ₁₈ aryl, where R ³ to R ^{7 can} also be linked to one another in cyclic compounds,
X ¹ to X ³ are anionic ligands which can be selected independently of one another, in particular F ^- , CL ^- , Br ^- , CN ^- , SCN ^- , R ³ O ^- , R ³ R ⁴ N ^- , (R ³ -R ⁷ ) allyl ^- , (R ³ -R ⁷ ) -cyclopentadienyl ^- , where the radicals R ³ to R ⁷ fulfill the definition already mentioned,
L ¹ to L ^{3 are} independently selectable neutral ligands, in particular CO, CO ₂ , R ³ NCO, R ₃ R ₄ C = CR ⁵ R ⁶ , R ³ C∼CR ⁴ , R ³ R ⁴ C = NR ⁵ , R ³ C∼N, R ³ OR ⁴ , R ³ SR ^4, NR ³ R ⁴ R ⁵ , PR ³ R ⁴ R ⁵ , AsR ³ R ⁴ R ⁵ , SbR ³ R ⁴ R ⁵ , the radicals R ³ to R ⁵ meet the definition already mentioned
and
m is 1 or 2. 11. The method according to claim 10, characterized in that compounds of the general formula (III) and / or (IV) with L ¹ and L ² = PR ³ R ⁴ R ⁵ are used as catalysts or catalyst precursors, where R ³ to R ⁵ correspond to the definitions given above, very particularly preferred radicals are aryl or alkyl, in particular secondary alkyl radicals or cycloalkyl radicals. 12. The method according to claim 11, characterized in that the following compounds are used as catalysts:
13. The method according to one or more of the preceding claims 1 to 12, characterized in that as ionic liquids ammonium hexa fluorophosphates, ammonium tetrafluoroborates, ammonium tosylates or Ammonium bisulfates are used or salt mixtures be used, the aluminum halides in combination with at least a quaternary ammonium halide and / or at least one quaternary Contain phosphonium halide. 14. The method according to claim 13, characterized in that as ionic Liquids pyridinium hexafluorophosphate, pyridinium tetrafluoroborate, Pyridinium bisulfate, 1-methyl-3-butylimidazolium hexafluorophosphate or combinations of aluminum chloride with 1-methyl-3-butylimidazo lium chloride, 1-methyl-3-ethylimidazolium chloride, N-butylpyridinium chloride and / or tetrabutylphosphonium halide can be used. 15. The method according to one or more of the preceding claims 1 to 14, characterized in that Kombina as ionic liquids ions of aluminum halide with mixtures of quaternary ammonium halides and / or quaternary phosphorus halides, and mixtures of ammonium hexafluorophosphates, ammonium tetrafluoroborates, Ammonium tosylates or ammonium bisulfates can be used can. 16. The method according to one or more of the preceding claims 1 to 15, characterized in that the reaction medium additionally an or contains several additives, which are selected independently from: Phosphorver bonds, amines, perfluorinated compounds, metal alkoxides or orga African solvents.