PL219008B1 - New compounds containing linear B-O-B-O-B bonds and process for the preparation of compounds with linear B-O-B-O-B bonds - Google Patents

Description

The present invention relates to new compounds containing linear B-O-B-O-B linkages and a method for the preparation of new compounds containing linear B-O-B-O-B linkages.

There are known compounds containing B-O-B bonds in their structure, which are used in many branches of modern chemistry, incl. as catalysts - Lewis acids in many reactions in organic chemistry, anion acceptors in batteries, or precursors of thermally stable porous and ceramic materials.

A number of compounds containing the cyclic B-O-B-O-B bond system are known from the literature.

A commonly used method of synthesizing compounds containing a cyclic B-O-B-O-B bond system is the method disclosed by Brown (1), which consists in thermal or chemical dehydration (using desiccants) of boronic acids. In this process, in order to shift the equilibrium towards the products, it is necessary to remove the water from the system, most often in the form of an azeotrope with benzene or toluene or by means of drying agents, e.g. P4O10 or SOCI2, CaH2. With this method, it is practically impossible to obtain systems containing linear B-O-B-O-B bonding systems.

Cyclic compounds containing B-O-B-O-B bonds (boroxins) are obtained by the method disclosed by Goubeau (2) by reacting triorganoborates with boron oxide at 300 ° C. The disadvantage of this method is the use of pyrophoric organoborates.

Another method of obtaining cyclic compounds containing B-O-B-O-B bonds is the method of their preparation disclosed by Rathke (3) in the carbonylation reaction of a borane-tetrahydrofuran complex catalyzed by a small amount of borohydride. A variation of this method is the carbonylation method disclosed by Brown using dimethylsulfide (1). This process uses the toxic gas of carbon monoxide.

Linear compounds containing a single B-O-B system are known. Compounds containing such a system in their structure can be synthesized by the method disclosed by Komorowska (4) consisting in the controlled hydrolysis of chloroborates. In this method, in order to remove the strongly corrosive HCl, an amine should be used, which reacts with an acid to form ammonium hydrochloride. The necessity of its separation as well as the acid evolution itself are disadvantages of this method. At the same time, it is not possible to selectively obtain the desired product that is in equilibrium with the cyclic boroxin.

Maringgele, (5) describes the preparation of compounds containing single linear B-O-B linkages by reacting appropriate alcohols with sodium and then the resulting sodium alkoxides with boron trihalide. Compounds containing only a single B-O-B linkage are obtained by this method.

These types of products, in addition to the previously mentioned applications (catalysts - Lewis acids, porous structures), can be used due to the high susceptibility of BOB bonds to hydrolysis, as well as the ease of the reverse process - dehydration, in the synthesis of modern self-healing compounds and polymers, as well as precursors ceramics and nanomaterials.

The aim of the invention was to develop new compounds containing linear B-O-BO-B linkages and a method for the preparation of new compounds containing the B-O-B-O-B bond.

The subject of the invention is new compounds having a linear B-O-B-O-B bond system of the general formula 1.

wherein:

- R1, R2, R3, R4, R5, R6 are the same and are hydrogen or methyl - n takes the value 0 or 1

PL 219 008 B1

- R represents groups of formulas 2 or 3,

wherein R7 is H, CH3, Br

In a second aspect, the invention relates to a process for the preparation of novel compounds containing linear B-O-B-O-B linkages of general formula I in which:

- (R1, R2, R3, R4, R5, R6) are the same or different and are hydrogen, methyl or ethyl

- n takes the value 0 or 1

- R represents: a group of formula 2 or 3, phenyl substituted at any position by halogen, straight or branched acylic group containing from 1 to 5 carbon atoms, carbonyl or carboxyl group; halogen-substituted or unsubstituted linear or branched alkyl having from 2 to 8 carbon atoms; an alkenyl group having 2 to 8 carbon atoms; alkenyl having 2 to 8 carbon atoms substituted by halogen or phenyl; alkynyl group containing 2 to 8 carbon atoms, alkyne containing 2 to 8 carbon atoms substituted with alkyl group containing 2 to 8 carbon atoms, phenyl or halogen.

The process according to the invention for the preparation of compounds with linear B-O-B-O-B bonds of general formula 1, in which n, R1, R2, R3, R4, R5, R6 are as defined above, consists in the coupling reaction of vinyl oxoborates of general formula 4, in which

n, R1, R2, R3, R4, R5, R6 are as defined above with the corresponding substituted boronic acids of general formula 5,

HO. .OH Β ι

R (5), wherein R is as defined above, in the presence of a catalyst selected from known ruthenium (0) complexes and known ruthenium (II) hydride or boryl complexes.

A 1.2 to 6 fold excess of vinyl oxoborane is used in the reaction for each hydroxyl group in the boronic acid, preferably a 1.5 to 2 fold excess is used for each hydroxyl group.

In particular, ruthenium complexes selected from the group [chlorohydridocarbonyltris (triphenylphosphine) ruthenium (II)] of formula 6 are used as catalysts,

[RuHCl (CO) (PPh3) 3] (6)

[chlorohydridocarbonylbis (tricyclohexylphosphine) ruthenium (II)] of formula 7,

[RuHCl (CO) (PCy3) 2] (7) tetrafluoroborate [diacetonitrilehydridocarbonylbis (tricyclohexylphosphine) ruthenium (II)] of formula 8, [RuH (CO) (MeCN2) (PCy3) 2] [BF4] (8)

PL 219 008 B1

[chlorocatecholoborylbis (tricyclohexylphosphine) ruthenium (II)] of formula 9, [Ru (BO2C6H4) Cl (CO) (PCy3) 2] (9)

[dodecacarbonylectrirutene (0)] of formula 10.

[Ru3 (CO) 12] (10)

The catalysts are used in an amount of 0.5 to 5 mol% with respect to the boronic acid used, preferably in an amount of 1 to 2 mol%. After completion of the reaction, the catalyst is removed by conventional methods.

The synthesis reaction according to the invention is carried out in an organic solvent under an inert gas atmosphere at a temperature from 25 ° C to the boiling point of the reaction mixture, preferably at a temperature of 60-80 ° C, for 6-48 h, preferably 18-24 h.

When dodecacarbonylectrirutene (0) or chlorohydrinocarbonyltris (triphenylphosphine) ruthenium (II) is used as catalysts, the reaction can be carried out both in an inert gas and an oxygen atmosphere.

The reactions are carried out in a solvent selected from the group of aromatic hydrocarbons, chlorinated hydrocarbons, tetrahydrofuran, dioxane or mixtures thereof. Most preferably, the reaction is carried out in dioxane or tetrahydrofuran.

The process according to the invention enables the synthesis of compounds containing a linear B-O-B-O-B bond system with conversion of boronic acids generally not lower than 65%. This method makes it possible to obtain the crude product in a yield generally not less than 60% of theoretical yield.

The advantage of the process according to the invention for the preparation of compounds containing the B-O-BO-B bond system is the possibility of synthesizing compounds in which B-O-B-O-B has a linear form and does not enter the cyclic ring structure. It is a new group of compounds containing in their structure linear connections of oxygen and boron atoms in the B-O-B-O-B bond system.

The method according to the invention can be used to synthesize compounds containing various substituents on the central boron atom, including those sensitive to the action of factors such as water, acid or hydrogen.

Other advantages of the process according to the invention are: the use of small amounts of catalyst, high selectivity of the process, as the only products are compounds containing the B-O-B-O-B bond sequence and ethylene, no toxic, difficult to isolate or explosive by-products such as H2 or HCl. Only in a few cases is a small amount of vinyl oxborane homocoupling byproducts formed.

The invention is illustrated by the following examples, which do not exhaust all possible uses of the synthesis method according to the invention. The structure of the obtained compounds containing linear B-O-B-O-B bonds was confirmed using the techniques of nuclear magnetic resonance (NMR) spectroscopy using Varian XL 300 MHz and elemental analysis using Vario EL III.

P r z k ł a d I

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.019 g of chlorohydridocarbonyltris (triphenylphosphine) ruthenium (II) was placed, followed by 2 mL of dioxane, 0.12 g of phenylboronic acid and 0.34 g of 2-vinyl-1, 3,2-dioxaborinane. The reaction mixture was heated for twenty-four hours at 80 ° C. The conversion of boronic acid and the yield of the crude product was 100%. In order to remove the catalyst from the system, the reaction mixture was applied to a chromatography column containing hexamethyldisilazane-modified silica, and then the product was isolated using hexane / ethyl acetate (1/1) as eluent. Bis (1,3,2-dioxaborinanyl-2-oxa) phenylborate was obtained with a yield of 77% pure product.

¹ H NMR (300 MHz, CDCl ₃ ): δ = 2.04 (q, 2H, J (H, H) = 5.5 Hz, BOCH ₂ CH ₂ ), 4.16 (t, 4H, J (H, H) = 5.5 Hz , BOCH ₂ CH ₂ ), 7.31-7.47 (m, 3H, C ₆ ^), 7.75-7.78 (d, 2H, C ₆ H ₅ ) ppm ¹³ C NMR (75 MHz, CDCl ₃ ): δ = 27.9 (BOCH ₂ C6), 62.3 (BOCH ₂ CH ₂ ), 127.8 (C ₆ H ₅ ), 130.8 (CH), 132.3 (CH), 133.9 (c _{C 6 H 5} ) ppm ¹¹ B NMR (96 MHz, CDCl ₃ ): δ = 28.7, 37.4 ppm

Elemental analysis for (%) C12H17B3O6: C, 49.75; H, 5.91 Found: C, 50.01; H, 5.77

P r z x l a d II

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.019 g of chlorohydridocarbonyltris (triphenylphosphine) ruthenium (II) was placed, followed by 2 mL of dioxane, 0.136 g of (4-methylphenyl) boronic acid and 0.34 g of 2-vinyl -1,3,2-dioxaborinane. The mixture

The reaction was heated for twenty-four hours at 80 ° C. The conversion of boronic acid and the yield of the crude product was 100%. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. Bis (1,3,2-dioxaborinanyl-2-oxa) (4'-methylphenyl) borane was obtained with a yield of 74% of pure product.

¹ H NMR (300 MHz, CDCl3): δ = 1.98 (q, 4H, BOCH2CH2), 2.51 (s, 3H, CH 3), 3.89 (t, 8H BOCH2), 7.12 (br, 2H, C6H5), 7.56 (br , 2H, C6H4) ppm ¹³ C NMR (75 MHz, CDCl3): δ = 21.1 (CHs), 26.8 (BOCH2CH2), 62.0 (BOCH2), 128.2 (C ^ Hs), 133.4 (C ₆ H ₅ ), 140.0 ( C 6 H ₅₎ ppm ¹¹ B NMR (96 MHz, CDCl3): δ = 33.2, 41.7ppm

Elemental analysis for (%) C13H19B3O6: C, 51.41; H, 6.31 Found C, 51.11; H, 6.41

P r x l a d III

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.019 g of chlorohydridocarbonyltris (triphenylphosphine) ruthenium (II) was placed, followed by 2 mL of dioxane, 0.2 g of (4-bromophenyl) boronic acid and 0.34 g of 2 -vinyl-1,3,2-dioxaborinate. The reaction mixture was heated for twenty-four hours at 80 ° C. The conversion of boronic acid and the yield of the crude product was 100%. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. Bis (1,3,2-dioxaborinanyl-2-oxa) (4'-bromophenyl) borane was obtained with a yield of 71% of pure product.

¹ H NMR (300 MHz, CDCl 3): δ = 1.89 (q, 4H, BOCH2CH2), 4.02 (t, 8H BOCH2), 7.03 (br, 2H, C6H4, 7.47 (br, 2H, C6H4) ppm ¹³ C NMR ( 75 MHz, CDCl3): δ = 27.0 (BOCH-CH-), 62.1 (BOCH2) 112.0 (C6H5), 129.4 (C6H5), 133.0 (c ₆ H ₅ ) ppm ¹¹ B NMR (96 MHz, CDCl3): δ = 33.8, 41.8 ppm

Elemental analysis for (%) C12H16BrB3O6: C, 39.10; H, 4.38 Found C, 38.88; H, 4.20

P r x l a d IV

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.019 g of chlorohydridocarbonyltris (triphenylphosphine) ruthenium (II) was placed, followed by 2 mL of dioxane, 0.148 g of (E) -styrylboronic acid and 0.34 g of 2-vinyl 1,3,2-dioxaborinane. The reaction mixture was heated for twenty-four hours at 80 ° C. The conversion of boronic acid and the yield of the crude product was 89%. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. Bis (1,3,2-dioxaborinanyl-2-oxa) (E) -styryl) borane was obtained with a yield of 74% pure product.

¹ H NMR (300 MHz, CDCl3): δ = 1.84 (q, 4H, J (H, H) = 5.5 Hz, BOCH2CH2), 3.92 (t, 8H, J (H, H) = 5.5 Hz, BOCH-OH ;), 6.09 (d, 1H, PhCH = CH, J (H, H) = 18.3 Hz), 6.54 (d, 1H, PhCH = CH, J (H, H) = 18.3 Hz), 7.12-7.56 (5H , C6H5) ppm ¹³ C NMR (75 MHz, CDCl3): δ = 26.9 (BOCH2CH2), 61.7 (BOCH2), 129.1 (C6H4), 129.3 (C ₆ H4), 132.0 (C ₆ H4), 133.8 (C ₆ H4 ), 145.4 (Ph-CH = CH) ppm ¹¹ B NMR (96 MHz, CDCl3): δ = 33.3, 41.8 ppm

Elemental analysis for (%) C14H19B3O6: C, 53.26; H, 6.07. Found: C, 53.03; H, 5.89

P r z k ł a d V

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.019 g of chlorohydridocarbonyltris (triphenylphosphine) ruthenium (II) was placed, followed by 2 mL of dioxane, 0.162 g of (E) -4-methylstyrylboronic acid and 0.34 g of 2- vinyl-1,3,2-dioxaborinate. The reaction mixture was heated for twenty-four hours at 80 ° C. The conversion of boronic acid and the yield of the crude product was 89%. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. Bis (1,3,2-dioxaborinanyl-2-oxa) [(E) -4-methylstyryl] borane was obtained with a yield of 72% of pure product.

¹ H NMR (300 MHz, CDCl3): δ = 1.84 (q, 4H, J (H, H) = 5.5 Hz, BOCH2CH2), 3.92 (t, 8H, J (H, H) = 5.5 Hz, BOCH2CH2) 6.09 (d, 1H, PhCH = CH, J (H, H) = 18.3 Hz), 6.54 (d, 1H, PhCH = CH, J (H, H) =

18.3 Hz), 7.12-7.56 (5H, C6H5) ppm ¹³ C NMR (75 MHz, CDCl3): δ = 26.9 (BOCH2CH2), 61.7 (BOCH2), 129.1 (C6H4), 129.3 (C6H4), 132.0 (C ₆ H4 ), 133.8 (C ₆ H4), 145.4 (Ph-CH = CH) ppm ¹¹ B NMR (96 MHz, CDCl3): δ = 33.3, 41.8 ppm

Elemental analysis for (%) C14H19B3O6: δ, 53.26; H, 6.07. Found: C, 53.03; H, 5.89

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P r x l a d VI

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.019 g of chlorohydridocarbonyltris (triphenylphosphine) ruthenium (II) was placed, followed by 2 mL of dioxane, 0.12 g of phenylboronic acid and 0.47 g of 4.4.5, 5-tetramethyl-2-vinyl-1,3,2-dioxaborolane. The reaction mixture was heated for twenty-four hours at 80 ° C. The conversion of boronic acid and the yield of the crude product was 96%. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. Bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl-2-oxa) phenylborate was obtained with a yield of 65% pure product.

¹ H NMR (300 MHz, CDCl 3): δ = 1.26 (s, 12H, CH3), 1.28 (s, 12H, CH3) 7.37-7.52 (m, 3H, C6H5), 7.79-7.82 (d, 2H, C6H5) ppm ¹³ C NMR (75 MHz, CDCl3): δ = 24.9 (CH3), 83.8 (BOC (CH3) ₂ ), 127.8 (& Η ₅ ), 131.2 (& Η ₅ ), 132.2 (C ₆ H ₅ ), 134.7 (cCaH ) ppm ¹¹ B NMR (96 MHz, CDCl3): δ = 31.0, 39.2 ppm

Elemental analysis for (%) C18H129B3O6: C, 57.83, H, 7.82 Found: C, 57.70, H, 7.98

P r o x l a d VII

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.019 g of chlorohydridocarbonyltris (triphenylphosphine) ruthenium (II) was placed, followed by 2 mL of dioxane, 0.2 g of (4-bromophenyl) boronic acid and 0.47 g of 4 , 4,5,5-tetramethyl-2-vinyl-1,3,2-dioxaborolane. The reaction mixture was heated for twenty-four hours at 80 ° C. The conversion of boronic acid and the yield of the crude product was 96%. Product isolation and catalyst removal were carried out according to the procedure described in Example I. Bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl-2-oxa) (4'-bromophenyl) borane was obtained with a yield of 60% pure the product.

¹ H NMR (300 MHz, CDCl 3): δ = 1.27 (s, 12H, CH3), 1.33 (s, 12H, CH3) 7.32-7.35 (br, 2H, C6H4), 7.71-74 (br, 2H, C6H4) ppm ¹³ C NMR (75 MHz, CDCl3): δ = 24.9 (CH3), 84 (BOC / CH ;,)), 116.0 (C5H4), 129.4 (C6H4), 132.2 (C6H4) ppm ¹¹ B NMR (96 MHz, CDCl3 ): δ = 32.6, 40.9 ppm

Elemental analysis for (%) C18H28BrB3O6: C, 47.75, H, 6.23 Found: C, 47.54, H 6.31

P r x l a d VIII

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.019 g of chlorohydridocarbonyltris (triphenylphosphine) ruthenium (II) was placed, followed by 2 mL of dioxane, 0162 of (E) -4-methylstyrylboronic acid and 0.47 g of 2-vinyl -1,3,2-dioxaborinane. The reaction mixture was heated for twenty-four hours at 80 ° C. The conversion of boronic acid and the yield of the crude product was 87%. Product isolation and catalyst removal were carried out according to the procedure described in Example I. Bis (4,4,5,5-tetramethyl-1,3,2-dioxaboroyl-2-oxa) [(E) -4-methylstyryl] borane was obtained with a yield of 59%. pure product.

¹ H NMR (300 MHz, CDCl3): δ = 1.19 (s, 12H, CH3), 1.26 (s, 12H, CH3), 2.27 (3H, s, CH2), 6.006.08 (d, 1 H, PhCH = CH , J (H, H) = 18.4 Hz), 6.64 (d, 1H, PhCH = CH, J (H, H) = 18.4 Hz) 7.00-7.08 (m, 2H, C6H4), 7.44-7.48 (m, 2H , C6H4) ppm ¹³ C NMR (75 MHz, CDCl3): δ = 21.2 (CH3C6H4) 24.3 (CH3), 83.5 (BOC (CH3126.4 (C5H4), 129.4 (C6H4), 134.5 (C6H4), 137.8 (C6H4) , 148.7 (Ph-CH = CH) ppm ¹¹ B NMR (96 MHz, CDCl3): δ = 32.6, 39.9 ppm

Elemental analysis for (%) C21H33B3O6: C, 60.94, H, 8.04 Found, C, 61.13, H 8.29

P r x l a d IX

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.014 g of [chlorohydridocarbonylbis (tricyclohexylphosphine) ruthenium (II)] was placed under an inert atmosphere, followed by 2 mL of dioxane, 0.12 g of phenylboronic acid and 0.34 g of 2 -vinyl-1,3,2-dioxaborinate. The reaction mixture was heated for twenty-four hours at temperature

80 ° C. The conversion of boronic acid and the yield of the crude product was 84%. In the post-reaction mixture, there were also observed traces of the by-product - bisborylethene, formed in the competitive reaction of homo-coupling of vinyl oxoborane catalyzed with the same complex. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. Bis (1,3,2-dioxaborinanyl-2-oxa) phenylborate was obtained with a yield of 51% of pure product. The result of the identification analysis was identical to that in example I.

PL 219 008 B1

P r z k ł a d X

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.017 g of tetrafluoroborate [diacetonitrylhydridocarbonylbis (tricyclohexylphosphine) ruthenium (II)] was placed under an inert atmosphere, followed by 2 mL of dioxane, 0.12 g of phenylboronic acid and 0.34 g of phenylboronic acid. g 2-vinyl-1,3,2-dioxaborinate. The reaction mixture was heated for twenty-four hours at 80 ° C. The conversion of boronic acid and the yield of the crude product was 84%. In the post-reaction mixture, there were also observed traces of the by-product - bisborylethene, formed in the competitive reaction of homo-coupling of vinyl oxoborane catalyzed with the same complex. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. Bis (1,3,2-dioxaborinanyl-2-oxa) phenylborate was obtained with a yield of 51% of pure product. The result of the identification analysis was identical to that in example I.

P r z x l a d XI

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.025 g of dodecacarbonyl-trirutene (0) was placed under an inert gas atmosphere, followed by 2 mL of dioxane, 0.12 g of phenylboronic acid and 0.34 g of 2-vinyl-1, 3,2-dioxaborinane. The reaction mixture was heated for twenty-four hours at 80 ° C. The conversion of boronic acid and the yield of the crude product was 91%. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. The bis (1,3,2-dioxaborinanyl-2-oxa) phenylborate was obtained with a yield of 64% of pure product. The result of the identification analysis was identical to that in example I.

P r x l a d XII

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.017 g of [chlorocatecholoborylbis (tricyclohexylphosphine) ruthenium (II)] was placed under an inert atmosphere, followed by 2 mL of dioxane, 0.12 g of phenylboronic acid and 0.34 g 2-vinyl-1,3,2-dioxaborinate. The reaction mixture was heated for twenty-four hours at 80 ° C. The conversion of boronic acid and the yield of the crude product was 95%. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. Bis (1,3,2-dioxaborinanyl-2-oxa) phenylborate was obtained with a yield of 70% of pure product. The result of the identification analysis was identical to that in example I.

Literature

1. H. C. Brown, T. E. Cole, Organometallics, 1985, 4, 816

2. V. J. Goubeau, H. Keller, Z. Anorg. Chem. 1951, 267, 1

3. M. W. Rathke, H. C. Brown, J. Am. Chem. Soc., 1966, 88, 2606

4. C. M. Komorowska, K. Niedenzu, W. Weber, Inorg. Chem., 1990, 29, 289

5. W. Maringgele, A. Meller, M. Noltemeyer, G. M. Sheldrick, Z. Anorg. Allg. Chem., 1986, 536, 24

Claims (6)

New compounds containing linear B-O-B-O-B linkages of general formula 1. (1) in which: - R1, R2, R3, R4, R5, R6 are the same and are hydrogen or methyl - n takes the value 0 or 1 PL 219 008 B1 - R represents groups of formulas 2 or 3, (2) in which R7 is H, CH3, Br 2. A method for the preparation of compounds for the preparation of compounds with linear B-O-B-O-B linkages of the general formula 1 in which: - (R1, R2, R3, R4, R5, R6) are the same or different and are hydrogen, methyl or ethyl - n takes the value 0 or 1 - R is: phenyl substituted at any position by halogen, straight or branched acyl group containing 1 to 5 carbon atoms, carbonyl or carboxyl; halogen-substituted or unsubstituted linear or branched alkyl having from 2 to 8 carbon atoms; an alkenyl group having 2 to 8 carbon atoms; alkenyl having 2 to 8 carbon atoms substituted by halogen or phenyl; alkynyl group containing 2 to 8 carbon atoms, alkyne containing 2 to 8 carbon atoms substituted with alkyl group containing 2 to 8 carbon atoms, phenyl or halogen; a group of formula 2 or 3, (2) in which R7 is H, CH3, Br, characterized by the coupling reaction of vinyloxoborates of general formula 4, (4) Wherein n, R1, R2, R3, R4, R5, R6 are as defined above with the corresponding substituted boronic acids of general formula 5, HCk. OH D And ^R (5), wherein R is as defined above, in the presence of a catalyst. 3. The method according to p. 2. The method of claim 2, characterized in that the catalyst is a compound selected from known ruthenium (0) complexes and known ruthenium (II) hydride or boryl complexes, in particular a compound selected from the group [chlorohydridocarbonyltris (triphenylphosphine) ruthenium (II)], [chlorohydridocarbonylbis (tricyclohexylphosphine) ) ruthenium (II)], tetrafluoroborate [diacetonitrilehydridocarbonyl-bis (tricyclohexylphosphine) ruthenium (II)], [chlorocatecholoborylbis (tricyclohexylphosphine) ruthenium (II)], [dodecacarbonylectrutene (0)]. 4. The method according to p. 3. A method according to claim 3, characterized in that the catalyst is a compound selected from the group [chlorohydridocarbonyltris (triphenylphosphine) ruthenium (II)], [chlorohydridocarbonylbis- (tricyclohexylphosphine) ruthenium (II)], tetrafluoroborate [diacetonitrylhydridocarbonylbis (triphenylphosphine) [chlorocatecholoborylbis (tricyclohexylphosphine) ruthenium (II)], [dodecacarbonyl electrirutene (0)]. 5. The method according to p. A process as claimed in any of the preceding claims, characterized in that the catalyst is used in an amount of 0.5 to 5 mol% with respect to the boronic acid used. 6. The method according to p. 5. The process of claim 5, characterized in that the catalyst is used in an amount of 0.5 to 5 mol%.