PL215709B1 - New boric acid esters and a new process for obtaining of boric acid esters - Google Patents

Description

The subject of the invention is new esters of boric acid and a new method of obtaining new and known esters of boric acid of the general formula 1.

The method of obtaining boric acid esters, known since the 1940s (LH Thomas, J. Chem. Soc., 1946, 820), is based on the equilibrium esterification of boric acid or its anhydride with appropriate alcohols as well as the trans-esterification reaction between boric acid ester, and other alcohol. In this process, in order to shift the equilibrium towards the products, it is necessary to remove water from the system, most often in the form of an azeotrope with benzene or toluene, or with the use of desiccants, e.g. anhydrous copper (II) sulfate. In the case of azeotropic drying, it is necessary to use an excess of alcohol in relation to boric acid or anhydride, because alcohols also form azeotropes with aromatic solvents (benzene, toluene). Reaction products often contain by-products (e.g. boroxins). which can make it difficult to isolate the actual product. In this reaction, only esters with the same alkoxy substituents attached to the boron atom are obtained, which significantly limits the applicability of this method to the synthesis of more complex esters.

There is also known (W. Gerrard, M. F. Lappert, J. Chem. Soc., 1951, 2545) the method of synthesizing boric acid esters by reacting chloroborates with alcohols. The disadvantages of this method are: the released hydrogen chloride, which must be removed, for example, by binding with an amine in the form of ammonium hydrochloride and the need to separate the product from the resulting ammonium hydrochloride.

Boric acid esters are also obtained by reacting alcohols with boron trihydride. Boron trihydride is a difficult to use reagent because of its volatility and high reactivity. In this process, hydrogen is a by-product which further complicates the synthesis. This method allows the synthesis of boric acid esters - with the same alkoxy substituents. (Y. Masuda, Y. Nunokawa, M. Hoshi, A. Aresa, Chem. Lett., 1992, 349).

Another known method of obtaining boric acid esters is the reaction of alcohols with sodium borohydride. Sodium borohydride is flammable and very sensitive to moisture, which requires special procedures and complicates the synthesis process. Also, this method makes it possible to obtain only boric acid esters - with the same alkoxy substituents (M. Pineschi, F. Bertolini, P. Crotti, F. Macchia, Org. Lett. 2006, 8, 2627).

Boric acid esters are reagents susceptible to nucleophilic attack by organolithium or organomagnesium compounds. As a result of these reactions, esters of boronic acids are obtained, which in turn are used as reagents in the Suzuki coupling, a reaction used in the synthesis of structured organic compounds, many of which are antibiotics, herbicides, fungicides or analogues of naturally occurring compounds.

Boric acid esters as mild syn-stereoselective ring opening reagents in epoxides and aziridines find use in reactions for the preparation of hydroxyphenols.

In syntheses where competitive reactions between the reactants and the OH- group are possible but undesirable, esterification of these alcohols with boric acid is used to protect the hydroxyl groups. The thus blocked groups can be readily deprotected after the end of the synthesis, with the restoration of the free hydroxyl groups by hydrolysis.

Boric acid esters are used in nanotechnology as reagents enabling the incorporation of B2O3 into the structure of nanocomposites and nanotubes, the presence of which in composites increases the resistance to solvents and chemicals, and also creates potential applications of these materials in nanoelectronics.

The aim of the invention was to develop new esters of boric acid and a new selective method for the preparation of new and known esters of boric acid, in particular esters containing various alkoxy substituents, one of which is incorporated in the coupling of vinyl oxoborates with alcohols.

The invention relates to new boric acid esters of the general formula I.

h ₂ every h ₂ c because K ₂ CO r

0)

Wherein R represents groups of formulas 2, 3, 4

In a second aspect, the invention relates to a new process for the preparation of new and known boric acid esters of the general formula 1 h ₂ c ~ o H ₂ C bo

H ₂ O C ^_ r (1) wherein R represents: a linear or branched alkyl having from 1 to 15 carbon atoms, or cycloalkyl having from 3 to 20 carbon atoms, or a group of formulas 2, 3, 4.

The process according to the invention for the preparation of substituted boric acid esters of the general formula 1, in which R is as defined above, consists in the coupling reaction of the vinyl oxoborate of the general formula 5 h ₂ at h ₂ cbh ₂ which

(5) with the appropriate substituted alcohols of general formula 6,

R-OH (6) wherein R is as defined above in the presence of a catalyst selected from ruthenium (II) hydride or boryl complexes or ruthenium (0) complexes. The reaction is carried out in a 1.2-6 fold excess of vinylocarbane over the alcohol, preferably in a 2-3 fold excess.

The catalysts used are ruthenium complexes selected from the group [chlorohydridocarbonyltris (triphenylphosphine) ruthenium (II)] of formula 7 [chlorohydrinocarbonylbis (tricyclohexylphosphine) ruthenium (II)] of formula 8, [chlorohydridocarbonylbis (tri-isophosphine) ruthenium] of formula 9, tetrafluoroborate [diacetonitrilehydridocarbonylbis (tricyclohexylphosphine) ruthenium (II)] of formula 10, [chlorocatecholoborylbis (tricyclohexylphosphine) ruthenium (II)] of formula 11 [dodecacarbonylectrirutene) of formula 12 (0.

[RuHCl (CO) (PPh3) 3] (7)

[RuHCl (CO) (PCy3) 2] (8)

[RuHCl (CO) (PiPr3) 2] (9)

[RuH (CO) (MeCN2) (PCy3) 2] [BF4] (10)

[Ru (BO2C6H4) Cl (CO) (PCy3) 2] (11)

[RU3 (CO) 12] (12)

The catalysts are used in an amount of 0.5 to 5 mol% with respect to the substituted alcohol 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 of 25-130 ° C, preferably 60-80 ° C, for 6-48 h, preferably

18-24 h. In the case of using the catalysts chlorohydrinocarbonyltris (triphenylphosphine) ruthenium (II) or dodecacarbonylectrutene (0), the reaction can be carried out both in an inert gas and an oxygen atmosphere.

PL 215 709 B1

The reactions are carried out in a solvent selected from the group: aliphatic hydrocarbons with a chain containing from 5 to 9 carbon atoms, aromatic hydrocarbons, cyclohexane, chlorinated hydrocarbons, tetrahydrofuran, dioxane or mixtures thereof. Due to the reversibility of the esterification reaction, it is advisable to use dehydrated solvents. Preferably, the reaction is carried out in a solvent selected from the group of: benzene, toluene, xylenes, aliphatic hydrocarbons having a chain of 5 to 9 carbon atoms, dichloroethane or dioxane and mixtures thereof. Most preferably, the reaction is carried out in toluene, dichloroethane or dioxane.

The process according to the invention allows the synthesis of boric acid esters of the general formula I with an alcohol conversion generally not lower than 70%. The yield of the crude product was not less than 65% of theory.

The advantage of obtaining boric acid esters by the process of the invention is the possibility of synthesizing esters containing in their structure simultaneously different alkoxy substituents directly attached to the boron atom. With the known methods for the synthesis of boric acid esters, the preparation of such unsymmetrical products is very difficult or practically impossible to achieve.

The method according to the invention can be used to synthesize esters containing complex alkoxy residues, which can additionally be functionalized with various groups sensitive to 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 (the only products are boric acid esters and ethylene), no toxic, difficult to isolate or explosive by-products such as H2 or HCl, only sometimes a small amount is produced. amount of by-products of vinylborate homocoupling.

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 boric acid esters was confirmed using the techniques of: gas chromatography combined with a mass spectrometer (GCMS) or nuclear magnetic resonance spectroscopy (NMR).

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 under an inert atmosphere, followed by 2 mL of toluene, 0.074 g of butan-1-ol and 0.22 g of 2-vinyl. -1,3,2-dioxaborinane. The reaction mixture was heated for twenty-four hours at 80 ° C. The alcohol conversion and crude product yield 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. 2-butoxy-1,3,2-dioxaborinane was obtained in a yield of 78% of pure product.

¹ H NMR (300 MHz, CDCl3): δ = 1. (t, 3H, CH3), 1.78 (q, 2H, CH2CH3), 1.92 (qu, 2H, BOCH2CH2CH2O, J (H, H) = 5.5 Hz), 2.16 (CH2CH2CH3), 3.85 (t, 2H, C (CH _{2) 2} CH 3, J (H, H = 4.6), 4.03 (t, 4Η, BOCH2CH2CH2O, J (H, H) = 5.5) ppm

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 toluene, 0.074 g of butan-1-ol and 0.22 g of 2-vinyl-1.3. , 2-dioxaborinate. The reaction mixture was heated for twenty-four hours at 80 ° C. The alcohol conversion and crude product yield was 100%. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. 2-butoxy-1,3,2-dioxaborinane was obtained with a yield of 76% of pure product. The result of the identification analysis was identical to that in example I.

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 under an inert atmosphere, followed by 2 mL of toluene, 0.088 g of 3-methyl-butan-1-ol and 0.22 g of 2-wine-1,3,2-dioxaborinate. The reaction mixture was heated for twenty-four hours at 80 ° C. The alcohol conversion and crude product yield were 100%. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. 2- (3'-methylbutoxy) -1,3,2-dioxaborinane was obtained with a yield of 71% of pure product.

¹ H NMR (300 MHz, CDCl 3): δ = 0.82 (d, 6 H, CH 2 CH 2 HM 1.37 (m, 1 H CH ₂ CH (CH 3) ₂ ), 1.81 (br, CH ₂ CH (CH 3) ) 2), 1.88 (qu, 2H, BOCH ₂ CH ₂ CH ₂ O), 3.74 (t, 2H, BOCH ₂ CH ₂ CH (CH3) ₂ ), 3.97 (BOCH2CH ₂ CH ₂ O) ppm

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 charged under an inert atmosphere, followed by 2 mL of toluene. 0.116 g of heptan-1-ol and 0.22 g of 2-vinyl-1,3,2-dioxaborinate. The reaction mixture was heated for twenty-four hours at 80 ° C. The alcohol conversion and crude product yield were 98%. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. Heptyloxy-1,3,2-dioxaborinane was obtained with a yield of 75% pure product.

¹ H NMR (300 MHz, CDCl 3): δ = 0.87 (t, 3H, CH 3), 1.28 (br, 6H, CH 2 Cl 2 Cl Cl Cl Cl 2), 1.54 (qu, 2H, CH 2 Hg), 1.76 (br, 2H, CH2 Hn), 1.93 (BOCH ₂ CHbCH ₂ O) 3.84 (t, 2H, BOCH2C6H13), 4.03 (BOCH2CH2CH2O) ppm

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 under an inert gas, followed by 2 mL of toluene, 0.100 g of cyclohexanol and 0.22 g of 2-vinyl-1,3. , 2-dioxaborinate. The reaction mixture was heated for twenty-four hours at 80 ° C. The alcohol conversion and crude product yield were 100%. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. 2-cyclohexyloxy-1,3,2-dioxaborinane was obtained with a yield of 67% of pure product.

¹ H NMR (300 MHz, CDCl 3): δ = 1.26 (m, 4H, Ο4), 1.51 (m, 2H, Ο4), 1.76-1.92 (br, 4H, C6H11, 2H BOCH2CH2CH2O), 3.83 (1H, OC6H11), 4.02 (t, 4H BOCHhCH ^ HhO, J (H, H) = 5.5 Hz) ppm

P r x l a d VI

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.019 g of chlorohydridocarbonylbis (tricyclohexylphosphine) ruthenium (II) was placed under an inert atmosphere, followed by 2 mL of toluene, 0.100 g of cyclohexanol and 0.22 g of 2-vinyl-1,3. , 2-dioxaborinate. The reaction mixture was heated for twenty-four hours at 80 ° C. The alcohol conversion and crude product yield were 100%. In the post-reaction mixture, there were also observed traces of the by-product - bisborylethene, formed in the competitive reaction of vinylborane homo-coupling catalyzed with the same complex. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. 2-cyclohexyloxy-1,3,2-dioxaborinane was obtained with a yield of 61% of pure product. The result of the identification analysis was identical to that in example 5.

P r o x l a d VII

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.024 g of tetrafluoroborate [diacetonitrylhydridocarbonylbis (tricyclohexylphosphine) ruthenium (II)] was placed under an inert atmosphere, followed by 2 mL of dichloroethane, 0.100 g of cyclohexanol and 0.22 g of 2-vinyl cyclohexanol and 0.22 g of tetrafluoroborate. 1,3,2-dioxaborinane. The reaction mixture was heated for twenty-four hours at 80 ° C. The alcohol conversion and crude product yield were 87%. In the post-reaction mixture, there were also observed traces of the by-product - bisborylethene, formed in the competitive reaction of vinylborane homo-coupling catalyzed with the same complex. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. 2-cyclohexyloxy-1,3,2-dioxaborinane was obtained with a yield of 54% of pure product. The result of the identification analysis was identical to that in example 5.

P r x l a d VIII

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.0097 g of chlorohydridocarbonylbis (trisopropylphosphine) ruthenium (II) were placed under an inert atmosphere, followed by 2 mL of toluene, 0.100 g of cyclohexanol and 0.22 g of 2-vinyl-1,3. , 2-dioxaborinate. The reaction mixture was heated for twenty-four hours at 80 ° C. The alcohol conversion and crude product yield were 100%. In the post-reaction mixture, there were also observed traces of the by-product - bisborylethene, formed in the competitive reaction of vinylborane homo-coupling catalyzed with the same complex. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. 2-cyclohexyloxy6 was obtained

PL 215 709 B1

-1,3,2-dioxaborinane with a yield of 58% of pure product. The result of the identification analysis was identical to that in example 5.

P r x l a d IX

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.032 g of dodecacarbonyl-trirutene (0) was placed under an inert atmosphere, followed by 2 mL of dioxane, 0.100 g of cyclohexanol and 0.22 g of 2-vinyl-1,3,2-dioxaborinane. . The reaction mixture was heated for twenty-four hours at 80 ° C. The alcohol conversion and crude product yield were 100%. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. 2-cyclohexyloxy-1,3,2-dioxaborinane was obtained in a yield of 65% pure product. The result of the identification analysis was identical to that in example 5.

P r z k ł a d X

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.017 g [chlorocatecholoborylbis (tricyclohexylphosphine) ruthenium (II)] was placed under an inert atmosphere, followed by 2 mL of dioxane, 0.100 g of cyclohexanol and 0.22 g of 2-vinyl-1.3 , 2-dioxaborinate. The reaction mixture was heated for twenty-four hours at 80 ° C. The alcohol conversion and crude product yield were 67%. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. 2-cyclohexyloxy-1,3,2-dioxaborinane was obtained with a yield of 43% pure product. The result of the identification analysis was identical to that in example 5.

P r z x l a d XI

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.019 g of chlorohydridocarbonyltris (triphenylphosphine) ruthenium (II) was placed under an inert gas atmosphere, followed by 2 mL of toluene, 0.108 g of benzyl alcool and 0.22 g of 2-vinyl-1, 3,2-dioxaborinane. The reaction mixture was heated for twenty-four hours at 80 ° C. The alcohol conversion and crude product yield were 82%. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. 2-benzyloxy-1,3,2-dioxaborinane was obtained with a yield of 58% of pure product.

¹ H NMR (300 MHz, CDCl 3): δ = 1.88 (qu, 2H, BOC 2 CH ₂ , J (H, H) = 5.5 Hz), 4.25 (t, 4H, BOCI ± CH ₂ , J (H, H ) = 5.5 Hz), 4.86 (s. 2H, BOCH ₂ Ph), 7.31-7.46 (br, 5H, C6H5) ppm

P r z k ł a d d XII

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.019 g of chlorohydridocarbonyltris (triphenylphosphine) ruthenium (II) was charged under an inert atmosphere, followed by 2 mL of toluene. 0.122 g of 2-phenylethanol and 0.22 g of 2-vinyl-1,3,2-dioxaborinane. The reaction mixture was heated for twenty-four hours at 80 ° C. The alcohol conversion and crude product yield were 88%. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. 2- (2'-phenylethoxy) -1,3,2-dioxaborinane was obtained with a yield of 61% of pure product.

¹ H NMR (300 MHz, CDCl 3): δ = 1.90 (qu, 2H, BOCH ₂ CH ₂ CH ₂ O, J = 5.5 Hz), 2.78 (t, OCH ₂ CH ₂ Ph, J = 5.7 Hz), 3.89 ( t, 4H, BOCH ₂ CH ₂ Ph, J = 5.7 Hz), 4.03 (t, 4H, BOCH ₂ CH ₂ CH ₂ O, J = 5.5 Hz), 7.20-7.37 (br, 5H, C6H5) ppm

P r x l a d XIII

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.019 g of chlorohydridocarbonyltris (triphenylphosphine) ruthenium (II) was placed under an inert atmosphere, followed by 2 mL of toluene, 0.086 g of 4-penten-1-ol and 0.22 g of 2 -vinyl-1,3,2-dioxaborinate. The reaction mixture was heated for twenty-four hours at 80 ° C. The alcohol conversion and crude product yield were 84%. The isolation of the product and remove the catalyst was carried out according to the procedure described in Example I. The resulting 2- (4'pentenyloksy) -1,3,2-dioxaborinan 62% yield of the pure product ¹ H NMR (300 MHz, CDCl3): δ = 1.67 (m , 2H, H ₂ C = CHCH ₂ CH ₂ ), 2.02 (qu, 2H, BOCH-CH-CH-O, J = 5.5 Hz), 2.22 (t, 2H, H ₂ C = CHCH ₂ ), 3.78 (t , 2H, 3.72, H ₂ C = CHCH ₂ CCH ₂ CH ₂ ), 4.03 (t, 4H, BOCH-CH-CH-O, J = 5.5 Hz), 4.67 (dd, 1H, H ₂ C = CH, J (H, H) = 2.1, 10.8), 4.93 (dd, 1H, H ₂ C = CH, J (H, H) = 2.1, 16.2 Hz), 5.21 (br, 1H, CH _; = CH) ppm

MS (EI): m / z (%): 170 (1) [M +], 141 (5), 115 (100), 85 (37), 67 (36)

P r x l a d XIV

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.019 g of chlorohydridocarbonyltris (triphenylphosphine) ruthenium (II) was placed under an inert atmosphere, followed by 2 mL of toluene, 0.102 g of furfuryl alcohol and 0.22 g of 2- vinyl-1,3,2-dioxaborinate. The reaction mixture was heated for twenty-four hours at 80 ° C. The alcohol conversion and crude product yield were 54%. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. 2- (tetrahydrofuran-2'-yl) methoxy-1,3,2-dioxaborinane was obtained in 41% pure product yield.

¹ H NMR (300 MHz, ODOI3): δ = 1.73-1.96 (m, 4Η OH2OH2OH), 2.01 (qu, 2H, BOOH2OH2OH2O), 3.70-3.89 (m, 4H, OOI OHOOI ± ±), 4.00 (t, 4H , BOOH2OH2OH2O), 4.14 (q, 1H, OCH) ppm

MS (EI): m / z (%): 186 (1) [M +], 115 (10), 85 (18), 71 (100), 57 (7)

P r z y k l a d XV

In a 10 mL reactor equipped with a reflux condenser and a stirrer, 0.019 g of chlorohydridocarbonyltris (triphenylphosphine) ruthenium (II) was placed under an inert atmosphere, followed by 2 mL of toluene, 0.071 g of 3-hydroxypropanenitrile and 0.22 g of 2-vinyl-1 , 3,2-dioxaborinate. The reaction mixture was heated for twenty-four hours at 80 ° C. The alcohol conversion and crude product yield were 100%. Product isolation and catalyst removal were carried out according to the procedure described in Example 1. 3- (1 ', 3', 2'-dioxaxaborate-2'-yloxy) propanenitrile was obtained with a yield of 73% of pure product.

¹ H NMR (300 MHz, ODOI3): δ = 1.99 (qu, 2H, BOOH2OH2OH2O, J = 5.5 Hz), 2.60 (t, 2H ΟΗ ₂ ΟξΝ), 3.89 (t, 2H, ΟΙ ± ΟΗ ₂ ΟξΝ), 4.03 (t, 4H, BOOH ₂ OH ₂ OH ₂ O, J = 5.5 Hz) ppm ¹³ C NMR (75 MHz, ODOI3): δ = 26.3 (Ο ^ ΟξΝ), 27.1 (BOOH ₂ OH ₂ OH ₂ O), 57.9 (ΒΟΟΗ ₂ ΟΗ ₂ ΟξΝ), 62.8 (BOOH ₂ OH ₂ OH ₂ O), 117.6 (C = N) ppm ¹¹ B NMR (96 MHz, ODOI 3): δ = 28.7 ppm;

MS (EI): m / z (%): 156 (6) [M ⁺ +1], 140 (7), 125 (10), 115 (100), 98 (25), 85 (23), 71 ( 10). 54 (28);

Elemental analysis calculated for (%) O6H10BNO3: O, 58.74; H, 9.31; N, 9.04 found O, 58.88, H, 9.23, N, 9.18.

Claims (8)

1. Esters of boric acid of general formula 1. h ₂ cc) h ₂ c bo H ₂ C ^_ OR 0) in which: - R represents groups of the following formulas 2, 3, 4 2. The method of obtaining new and known esters of boric acid of general formula 1 h ₂ c ~ oh ₂ c bo H ₂ C “O r (1) in which: PL 215 709 B1 - R represents: linear or branched alkyl containing from 1 to 15 C atoms, or cycloalkyl containing from 3 to 20 C atoms or groups of the formulas 2, 3, 4, characterized by the coupling reaction of the corresponding vinyl oxboranes of general formula 5, h ₂ at h ₂ cbh ₂ with (5) with the corresponding substituted alcohols of general formula 6, R-OH (6) in which R is as defined above in an organic solvent in the presence of a catalyst selected from ruthenium (II) hydride or boryl complexes or ruthenium (0) complexes, the reaction being carried out in the presence of oxygen or in an inert gas depending on the resistance of the catalyst to oxygen. 3. The method according to p. 2. The process according to claim 2, characterized in that the catalysts are ruthenium complexes selected from the group [chlorohydridocarbonyltris (triphenylphosphine) ruthenium (II)], [chlorohydridocarbonylbis (tricycloliexylphosphine) ruthenium (II)], [chlorohydridocarbonylbis (triutiphosphine) ], tetrafluoroborate [diacetonitrile-dihydridocarbonylbis (tricyclohexylphosphine) ruthenium (II)], [chlorocatecholoborylbis (tricyclohexylphosphine) ruthenium (II)], [dodecacarbonylectrirutene (0)]. 4. The method according to p. The process of claim 2 or 3, characterized in that the catalyst is used in an amount of 0.5 to 5 mol% with respect to the substituted alcohol used. 5. The method according to p. The process of claim 4, wherein the catalyst is used in an amount of 1 to 2 mol% with respect to the substituted alcohol used. 6. The method according to p. 2, 3, 4 or 5, characterized in that the reaction is carried out in a solvent selected from the group: aliphatic hydrocarbons with a chain containing from 5 to 9 carbon atoms, aromatic hydrocarbons, cyclohexane, chlorinated hydrocarbons, tetrahydrofuran, dioxane or their mixtures 7. The method according to p. 6. The process as claimed in claim 6, characterized in that the reaction is carried out in a solvent selected from the group: benzene, toluene, xylenes, aliphatic hydrocarbons with a chain containing from 5 to 9 carbon atoms, dichloroethane, dioxane and mixtures thereof. 8. The method according to p. The process of claim 7, wherein the reaction is carried out in toluene, or dichloroethane or dioxane.