PL210895B1 - Method of obtaining substituted 1,3,5-tri(E) styrilo benzenes - Google Patents

Description

(12) PATENT DESCRIPTION (19) PL (11) 210895 (13) B1 (21) Application number: 386071 ^{(51) Int.Cl.}

C07C 15/52 (2006.01) (22) Date of notification: 12/09/2008 (54) Preparation of substituted 1,3,5-tri (E) -styrylbenzenes

(73) The right holder of the patent: UNIVERSITY OF ADAM MICKIEWICZ, (43) Application was announced: Poznan, PL March 15, 2010 BUP 06/10 (72) Inventor (s): BOGDAN MARCINIEC, Swarzędz, PL (45) The grant of the patent was announced: WIESŁAW PRUKAŁA, Poznań, PL 30.03.2012 WUP 03/12 (74) Representative: item. stalemate. Wojciech Lisiecki

PL 210 895 B1

Description of the invention

The subject of the invention is a new method for the synthesis of substituted 1,3,5-tri (E) -styrylbenzenes of the general formula 1.

The substituted 1,3,5-tri (E) -styrylbenzenes containing conjugated vinyl bonds are characterized by photophysical properties such as absorption in the visible range and a high molar extinction coefficient of fluorescence. They find practical application thanks to their photo-chemical and photoelectric properties.

The photoelectric and photoluminescent properties of 1,3,5-tri (E) -styrylbenzenes significantly depend on the content of particular types of trans- (E) and cis- (Z) bonds present in them. The position of the absorption and emission bands of light depends to a large extent on the content of a given type of Z or E bond in the molecule. Z bonds absorb at lower wave frequencies and are characterized by lower quantum efficiency, ie low secondary emission. E-type bonds absorb at higher wave frequencies and are characterized by high quantum efficiency. Thus, depending on the expected optoelectronic properties and the intended application, it is advisable to obtain these compounds with a strictly defined configuration and purity. Compounds containing a uniform type of bonds show relatively sharp emission bands, while their mixture and compounds containing both types of bonds in their structure may show a significant broadening of both absorption and emission bands.

Several methods are known for the synthesis of 1,3,5-tri (E) -styrylbenzenes. The known methods allow the synthesis of compounds characterized by a different degree of homogeneity of vinyl bonds in the molecule and a relatively low yield.

The literature (1) discloses a method of obtaining 1,3,5-tri (E) -styrylbenzene by reaction between 1,3,5-trimethylbenzene and benzylideneaniline in the presence of potassium tert-butoxide in DMF at 90-95 ° C. This reaction is characterized by a low yield of 14-19.5% of the E-isomer.

The literature discloses (2) a method using the so-called the Wittig reaction, the synthesis of 1,3,5-tris ((E) -4-bromostyryl) benzene by reacting 1,3,5-triformylbenzene with 4-bromophenylmethyl (triphenyl) phosphonium bromide in THF. The reaction was carried out in the presence of potassium carbonate and 18-crown-6 crown ether to give the mixture of the E and Z isomers with an overall yield of 71%.

There is known from the literature (3, 4, 5) a method for the preparation of 1,3,5-tri (E) -styrylbenzene or 1,3,5-tris ((E) -p-chlorostyryl) benzene consisting in the first stage of reaction between 1,3,5-tris (bromomethyl) benzene and triethyl phosphite in refluxing xylene, and then the obtained triphosphonic ester is reacted by a Wittig-Homer reaction with benzaldehyde (or p-chlorobenzaldehyde) in the presence of sodium methoxide. giving 1,3,5-tri (E) -styrylbenzene (or 1,3,5-tris ((E) -p-chlorostyryl) benzene) in an overall yield not exceeding 30%.

The aim of the invention was to develop a cheap and effective method for the preparation of the known substituted 1,3,5-tri (E) -styrylbenzenes.

The subject of the invention is a method of synthesizing substituted 1,3,5-tri (E) -styrylbenzenes of the general formula I, in which

- R is an atom: H, Cl or Br consisting of a desilylating coupling reaction in the presence of a desilylating coupling catalyst and an activator of the appropriate substituted 1,3-bis (styryl) tetramethyldisiloxane of the general formula 2,

GB 210 895 B1 CH ₃ of I and ^J

R

// - ŚFO-Si / ι ¹

R

CH ₃ CH ₃ (2) in which R is H, Cl, or Br, wherein R may be two identical or different atoms, with a suitable trihalobenzene of general formula 3, in which (3)

- X is iodine or bromine, where X may be the same or different atoms. The reaction is carried out in organic solvents under an inert gas atmosphere.

A compound selected from the group of palladium (0) complexes or palladium (II) and (IV) compounds is used as a catalyst for the desilylating coupling reaction.

Palladium (II) and (IV) compounds are also used as the desilylating coupling catalyst system in the presence of a suitable amount of a ligand selected from the group: phosphines, cyclic tertiary amines, in particular tris (2-methylphenyl) phosphine, (P (o- Tol) 3), Ph3PO, 1,4-diazabicyclo [2.2.2] octane (DABCO), triphenylphosphine (PPh3). These ligands can form in situ complexes with the catalyst compounds of the palladium.

It is preferable to use desilylating coupling catalysts selected from the group

[Pd (PPh3) 4], [Pd (dba) 2], [Pd2 (dba) 3], [Pd2 (dba) 3] xCHCl3, PdCl2, PdBr2, Pd (CH3COO) 2, Pd (OTf) 2,

[PdCl (n ₃ -C ₃ H ₅ )] ₂ , [PdCl ₂ (PhCN) ₂ ], [PdCl ₂ (PPh ₃ ) ₂ ] (COD) PdBr ₂ , [allylPdCl] ₂ , (PPh ₃ ) ₂ BnPdCl in in particular palladium (0) complex [Pd2 (dba) 3].

The desilylating coupling catalysts are used in an amount of 0.004 to 0.1 mole per mole of 1,3-bis (styryl) tetramethyldisiloxane.

It is particularly preferred to use approx. 0.02 mole of Pd2 (dba) 3 per mole of 1,3-bis (styryl) tetramethyldisiloxane.

The Si-C bond in 1,3-bis (styryl) tetramethyldisiloxanes is relatively stable and not very susceptible to reactions related to its homolysis, therefore it is necessary to use an activator in the reaction according to the invention.

The activators used are compounds selected from the group of: fluoride salts, Cs2CO3, Ag2O, CuJ, K2CO3, NaOH, KOH, NaH, (CH3) 3SiOK, (CH3) 3SiONa. In particular, it is preferable to use difluoro (trimethyl) silicon tris (diethylamino) sulfonate (TASF) or tetrabutylammonium fluoride (TBAF) as activators.

The activator is used in an amount of not more than 5 moles per mole of silicon bound in 1,3-bis (styryl) tetramethyldisiloxane, preferably 1.2 to 1.5 moles of activator per mole of silicon. The activator may be introduced simultaneously with all the reagents, but it is preferable to add it prior to the addition of the coupling desilylation catalyst.

It is preferable to use at least a two-fold molar excess of 1,3-bis (styryl) tetramethyldisiloxane over trihalobenzene. The lower excess or underflow leads to a significant reduction in yield and the presence of unreacted starting materials, which makes subsequent purification of the main reaction product difficult.

The desilylating coupling reactions according to the invention are carried out in low-polarity solvents, such as, in particular, dioxane, THF, diethyl ether, benzene, toluene, chlorobenzene, N-methylpyrrolidone, DMF or dimethoxyethane or a mixture thereof.

Due to the good solubility of the catalysts and activators and the ease of handling and low toxicity, it is preferable to use dioxane.

The reaction runs efficiently at a temperature of 20-140 ° C depending on the type of substrates used.

When 1,3-bis ((E) -4-bromostyryl) tetramethyldisiloxane is used, the efficiency of the process is strongly related to the temperature, as the temperature increases rapidly as the temperature increases.

Competing polymerization reactions, which affects the efficiency of the process as well as complicates the purification processes of the final product, which is the corresponding substituted 1,3,5-tri (E) -styrylbenzene.

Depending on the type of substrate used, it is preferable to use the following temperatures:

- triiodobenzene and 1,3-bis (E) -4-bromostyryl) tetramethyldisiloxane - temperatures ranging from 20-60 ° C.

- triiodobenzene and 1,3-bis (styryl) tetramethyldisiloxane or 1,3-bis (E) -4-chlorostyryl) tetramethyldisiloxane - temperatures ranging from 20-140 ° C.

- tribromobenzene and 1,3-bis (styryl) tetramethyldisiloxane or 1,3-bis (E) -4-chlorostyryl) tetramethyldisiloxane - temperatures in the range of 60-140 ° C.

- tribromobenzene and 1,3-bis (E) -4-bromostyryl) tetramethyldisiloxane - temperature approx. 60 ° C or slightly higher.

The synthesis reaction of the invention is carried out in a heated reactor under an atmosphere of dried inert gas.

In order to determine the moment of completion of the reaction, the conversion of 1,3-bis (styryl) tetramethyldisiloxane is checked by GC or GC-MS analysis, and if there are significant amounts of substrate, the reaction time is extended or a new portion of the coupling desilylation catalyst is added and the reaction time is extended until to obtain a conversion above 99%.

It is preferable to carry out the reaction with the following proportions between the reactants, desilylating coupling catalysts and solvents:

• 1 mol of 1,3-bis (styryl) tetramethyldisiloxane • 0.5 mol of the corresponding trihalobenzene • 2.4 mol of TBF • 10 liters of dioxane • 0.02 mol of Pd2 (dba) 3

After completion of the reaction, the product precipitated was filtered off and washed with tetrahydrofuran, and then the filtrate was purified, preferably on a silica gel column. The solvent is removed from the purified filtrate. The dry residue is the second part of the product. Both parts of the product are combined and dried.

A variation of the method according to the invention for the synthesis of substituted 1,3,5-tri (E) -styrylbenzenes of the general formula I, in which R is as defined above, is a method that involves the use of sequences (the so-called "one-pot" reaction ) two reactions: the silylating coupling of styrene or 4-halogenostyrene with 1,3-divinyl tetramethyldisiloxane, followed by the desilylating coupling reaction of the substituted 1,3-bis (styryl) tetramethyldisiloxane formed in the first step with a trihalogenobenzene of the general formula 3, where X is as given above importance.

The products obtained in the first reaction are among the starting materials in the second reaction. The products of the silylating coupling reaction may or may not be used in the subsequent desilylating coupling reaction without isolation from the reaction medium.

In the first step, the silylating coupling reaction of styrene or 4-halostyrene with 1,3-divinyl tetramethyldisiloxane is carried out in the presence of a silylating coupling catalyst in an organic solvent.

The silylation coupling catalyst used is a compound selected from the group: RuHCl (CO) (PPh3) 3 complex, ([RuH (CI) (CO) (PCy3) 2]), [RuCl2 (CO) 3] 2).

The silylating coupling catalysts are used in an amount of 0.01 to 0.2 moles per one mole of 1,3-divinyl tetramethyldisiloxane. For economic reasons, it is recommended to use about 0.02 mole of RuHCl (CO) (PPh3) 3 per one mole of 1,3-divinyl tetramethyldisiloxane, which amount allows the reaction to be carried out with optimal rate and yield. In the case of using RuHCI (CO) (PPh3) 3, the addition of CuCl as cocatalyst has a favorable influence on the course of the reaction, with the catalyst to cocatalyst ratio being in the range from 1: 1 to 1: 5. The addition of copper (I) chloride as a cocatalyst to the reaction mixture after approx. 5 minutes from its start, significantly accelerates the reaction rate and its efficiency. The most advantageous solution is to use a threefold excess of cocatalyst. The use of small amounts of catalyst leads to a significant slowing of the reaction and an increase in the amount of monosubstituted by-products.

The silylating coupling reaction is carried out in solvents with a boiling point higher than 70 ° C selected from the group: benzene, toluene, chlorobenzene, ether derivatives or a mixture thereof, preferably dioxane is used.

The reaction runs efficiently at 80-160 ° C (most often at 100 ° C).

PL 210 895 B1

In order to determine the moment of completion of the reaction, the conversion of 1,3-divinyl tetramethyldisiloxane is checked by GC or GC-MS analysis, and if there are significant amounts of substrate, the reaction time is extended or a new portion of the catalyst is added and the reaction time is extended until the conversion is above 99 %.

In the reaction, according to the method of the invention, an excess of styrene or 4-halostyrene is used in relation to 1,3-divinyl tetramethyldisiloxane. The ratio of styrene or 4-halostyrene to 1,3-divinyl tetramethyldisiloxane should be 3: 1 to 5: 1. It is advantageous to use an excess of about 4 times. With a larger excess, the reaction is faster, but the amount of styrene or halogenostyrene polymerization by-products increases, while a low excess leads to an increase in the amount of mono-styryl vinyl tetramethyldisiloxane derivatives, which significantly reduces the yields of both the first and second steps of the reaction sequence and makes subsequent purification of the main products difficult. The formation of a mono-substituted product in the first step particularly adversely affects the yield of the second step.

The synthesis reaction according to the invention is preferably carried out in a heated reactor under an atmosphere of dried inert gas. The substrates and the silylating coupling catalyst are dissolved, and then, after heating to ca. 100 ° C, the reaction is carried out with stirring until maximum conversion is obtained. If the conversion of 1,3-divinyl tetramethylsiloxane above 99% cannot be achieved due to e.g. uncontrolled loss of styrene or 4-halogenostyrene, it is advisable to add another portion of these reagents. A conversion below 99% adversely affects the course of the second stage.

If a cocatalyst is used in the reaction, it is introduced into the reaction medium only a few minutes after the reaction mixture has been heated to a temperature of about 100 ° C.

The course and efficiency of the silylation coupling reaction is significantly dependent on the type of catalysts and the relations between the reactants, as well as the silylation coupling catalysts and the process parameters. Smaller amounts of silylating coupling catalyst or cocatalyst as well as shorter reaction time result in the formation of significant amounts of monosubstituted product, which significantly affects the efficiency of the second step, i.e. the desilylating coupling, and therefore it is desirable to use parameters that effectively limit the formation of undesirable by-products.

It is preferred to carry out the reaction with the following proportions between the reactants, silylating coupling catalysts, and solvents:

• 1 mole of 1,3-divinyl tetramethyldisiloxane • 4 moles of the corresponding 4-halostyrene • 4 liters of dioxane • 0.02 moles of RuHCl (CO) (PPh3) 3 • 0.06 CuCl

The second step consists in the desilylating coupling reaction of the corresponding 1,3-bis (styryl) tetramethyldisiloxane obtained in the first step with the appropriate trihalobenzene of the general formula where X is as defined above, in the presence of a desilylating coupling catalyst and an activator in an organic solvent.

After the completion of the first stage, the appropriate trihalobenzene of the general formula 3, in which X is as defined above, the activator is introduced into the reaction mixture and diluted until the substrates are completely dissolved, then, after the substrates are completely dissolved, the desilylating coupling catalyst is added, followed by the second synthesis stage. carried out analogously to the above-described one-step synthesis between the appropriate 1,3-bis (styryl) tetramethyldisiloxane and the corresponding trihalobenzene using the above-described desilylating coupling catalysts, activators and parameters and procedures.

It is preferable to cool the post-reaction mixture to a temperature below 30 ° C after the first stage, which will allow more complete control of the feedstock feed.

The synthesis reaction according to the invention is preferably carried out in a heated reactor under an atmosphere of dried inert gas. To the reaction mixture obtained after the first stage, an activator and a sufficient amount of a solvent are added to make the starting materials complete, and then the catalyst is added, and after heating to a temperature of about 30 ° C, the reaction is carried out with stirring until maximum conversion is obtained.

PL 210 895 B1

The process according to the invention makes it possible to obtain substituted 1,3,5-tri (E) -styrylbenzenes containing a highly coupled double bond system with very high stereoselectivity (> 99% (E)) using relatively simple, cheap and chemically stable substrates.

A preferred embodiment of the invention, the use of the "one-pot" method, makes it possible to significantly simplify the process and shorten the synthesis time of substituted 1,3,5-tri (E) -styrylbenzenes, while only slightly reducing the final yields.

The synthesis of substituted 1,3,5-tri (E) -styrylbenzenes according to the present invention is shown in the following examples which illustrate the invention but do not limit its scope. A Varian Saturn 2100T (GC-MS) apparatus was used to measure the conversion of the substrates. The structure of the compounds obtained was confirmed by nuclear magnetic resonance (NMR) spectroscopy. IR absorption was measured in KBr with a Brucker ITS 113v spectrophotometer. Mass analysis (EI-MS) was performed on an AMD (Harpstedt, Germany) Intectra model 402 apparatus.

P r z k ł a d 1

In a 10 ml reactor equipped with a reflux condenser and a magnetic stirrer, under an argon atmosphere, were placed: 0.169 g (0.5 mmol) 1,3-bis ((E) -styryl) tetramethyldisiloxane 5.0 ml of dioxane 78.7 mg (0, 25 mmol) 1,3,5-tribromobenzene, 0.32 g (1.2 mmol) tetrabutylammonium fluoride (TBAF) and 9.16 mg (0.01 mmol) palladium complex [Pd2 (dba) 3]. The system was heated at 80 ° C for 16 h. The resulting product precipitate was filtered off and washed with tetrahydrofuran, and the filtrate was loaded onto a silica gel column. After completion of the separation, the eluent was evaporated and the recovered product was combined with the precipitate previously filtered off and dried in vacuo. 0.091 g of 1,3,5-tri (E) -styrylbenzene was obtained, which is 95% of theory.

Colorless precipitate; efficiency: 95%; mp = 200-203 ° C.

IR (KBr, cm ^-1 ): 3055.2, 3025.5, 2954.7, 2924.2, 1683.2, 1597.5, 1585.1, 1494.5, 1449.9, 1072.7, 961.4, 824.5,747.6, 690.6,533.7.

¹ H NMR (CDCl3): δ = 7.09 (d, J = 17.3 Hz, 3 H, C6H3-CH =), 7.18-7.39 (m, 18 H, C6H5-CH =), 7.57 (s, 3 H, C6H3 ).

MS (EI): m / z (%) = 384 (100), 362 (55), 360 (52), 282 (30), 265 (32), 205 (40), 203 (44), 178 (33 ), 165 (20), 152 (15), 115 (22), 103 (30), 91 (41), 77 (34);

(El): m / z cal. for C30H24: 384.1878; found: 384.1865.

P r z k ł a d 2

9.52 mg (0.01 mmol) of ruthenium complex [RuHCl (CO) (PPh3) 3], 2.0 ml of dried and de-oxygenated dioxane, 0.1 g are placed in a 10 ml reactor equipped with a reflux condenser and a magnetic stirrer under argon. (0.5 mmol) 1,3-divinyl tetramethyldisiloxane and 0.208 g (2.0 mmol) styrene. The system was placed in an oil bath and heated at 100 ° C under argon for 5 minutes. Then, 2.97 mg (0.03 mmol) of copper (I) chloride as a cocatalyst were added to the reaction mixture and the reaction was heated for another 24 h. The progress of the reaction was monitored by GC and GCMS analyzes until the 1,3-divinyl tetramethyl disiloxane had reacted completely (conversion over 99%). The mixture was then cooled to room temperature, and after cooling into the reaction vessel under argon, introduced: 3.0 ml of dioxane, 78.7 mg (0.25 mmol) of 1,3,5-tribromobenzene, 0.32 g (1.2 mmol) of tetrabutylammonium fluoride ( TBAF) and then, after the starting materials had dissolved, 9.16 mg (0.01 mmol) of palladium complex [Pd2 (dba) 3] was added. The system was placed back in the oil bath and, keeping the temperature at 80 ° C, left for 16 h. The resulting precipitate was filtered off, and the filtrate was loaded on a column filled with silica gel. After completion of the separation, the eluent was evaporated and the recovered product was combined with the previously filtered solid and dried in vacuo. The obtained 0.089 g of 1,3,5-tri (E) -styrylbenzene was 93% of theoretical yield.

Colorless precipitate; yield: 93%; mp = 200-203 ° C.

IR (KBr, cm ^-1 ): 3055.2, 3025.5, 2954.7, 2924.2, 1683.2, 1597.5, 1585.1, 1494.5, 1449.9, 1072.7, 961.4, 824.5, 747.6, 690.6, 533.7.

¹ H NMR (CDCl3): δ = 7.09 (d, J = 17.3 Hz, 3 H, C6H3-CH =), 7.18-7.39 (m, 18 H, C6H5-CH =), 7.57 (s, 3 H, C6H3 ).

MS (EI): m / z (%) = 384 (100), 362 (55), 360 (52), 282 (30), 265 (32), 205 (40), 203 (44), 178 (33 ), 165 (20), 152 (15), 115 (22), 103 (30), 91 (41), 77 (34);

(El): m / z cal. for C30H24: 384.1878; found: 384.1865.

PL 210 895 B1

P r z k ł a d 3

In the same conditions as in example 2, a reaction in the first step was carried out between 0.1 g (0.5 mmol) 1,3-divinyl tetramethyldisiloxane and 0.277 g (2.0 mmol) 4-chlorostyrene in the presence of 9.52 mg [RuHCl (CO) (PPh3) 3] and 2 ml of dioxane, and in the second step 78.7 mg (0.25 mmol) of 1,3,5-tribromobenzene, 3 ml of dioxane, 0.32 g of TBAF and 9.16 mg of [Pd2 (dba) 3] were used. The second stage was carried out at 80 ° C for 48 hours.

0.109 g of 1,3,5-tris ((E) -4-chlorostyryl) benzene was obtained (yield: 90%); as a yellow-green powder, mp = 216-220 ° C.

Yellow-green powder; efficiency: 90%; mp = 216-220 ° C.

IR (KBr, cm ^-1 ): 806.3, 841.7, 960.2, 1090.4, 1490.7, 1585.1, 1668.2, 2924.2, 2957.7, 3024.9.

¹ H NMR (CDCl3): δ = 7.09 (d, J = 15.9 Hz, 3 H, C6H3-CH =), 7.20-7.45 (m, 15 H, C6H4-CH =), 7.65 (s, 3 H, C6H3 ).

MS (EI): m / z (%) = 486 (8) [M ⁺ ], 364 (56), 350 (47), 220 (49), 205 (100), 73 (57); HRMS (EI): m / z calcd. C30H21 for ³⁵ Cl 3: 486.0709; found: 486.0694.

Literature

1. Siegrist, A.E .; Liechti, P .; Meyer, H.R .; Weber, K. Helv. Chim. Acta 1969, 52, 2521

2. Mehta, G .; Panda, G .; Sarma, P.V.V.S. Tetrahedron Lett. 1998, 39, 5835

3. Malkes, L.Y .; Kovalenko, N.P. Zh. Org. Khim. 1966, 2, 297.

4. Malkes, L.Y .; Kovalenko, N.P. Zh. Org Khim. 1970, 4, 1455.

5. Kovalenko, N.P .; Heifec, L.Y .; Malkes, L.Y. Zh. Org Khim. 1971, 7, 2149.

Claims (24)

Patent claims 1. A method for the preparation of 1,3,5-tri (E) -styrylbenzenes of the general formula I, in which: -R is an atom: H, Cl or Br, characterized in that a desilylating coupling reaction is carried out between an appropriately substituted 1,3-bis (styryl) tetramethyldisiloxane of the general formula II, wherein Z is H, Cl or Br, with Z can be two atoms that are the same or different, and with a suitable trihalobenzene of the general formula 3, wherein - X is iodine or bromine. Wherein X may be three identical or different atoms, in the presence of a desilylating coupling catalyst and an activator in an organic solvent under an inert gas atmosphere. 2. The method according to p. The process of claim 1, wherein the desilylating coupling catalyst is a compound selected from the group: palladium (0) complexes or palladium (II) and (IV) compounds. 3. The method according to p. 2. The process of claim 2, wherein the desilylating coupling catalyst is compounds selected from the group [Pd (PPh3) 4], [Pd (dba) 2], [Pd2 (dba) 3], [Pd2 (dba) 3] xCHCl3, PdCl2, PdBr ₂ , Pd (CH ₃ COO) ₂ , Pd (OTf) ₂ , [PdCl (n ₃ -C ₃ H ₅ )] ₂ , [PdCl ₂ (PhCN) ₂ ], [PdCl ₂ (PPh ₃ ) ₂ ] (COD) PdBr ₂ , [allyl PdCl] 2, (PPh3) 2BnPdCl. 4. The method according to p. The process of claim 3, wherein the desilylating coupling catalyst is [Pd2 (dba) 3]. 5. The method according to p. The process of claim 1, wherein palladium (0), (II) and (IV) compounds are used as the desilylating coupling catalyst in the presence of a ligand selected from the group: phosphines, cyclic tertiary amines. 6. The method according to p. 3. The process according to claim 3, characterized in that the ligands are a compound selected from the group: tris (2-methylphenyl) phosphine, (P (o-tol) 3), Ph3PO, 1,4-diazabicyclo [2.2.2] octane, triphenylphosphine (PPh3 ). Method according to claim 1, 2 or 6, characterized in that the activators are compounds selected from the group: fluoride salts, Cs2CO3, Ag2O, CuJ, K2CO3, NaOH, KOH, NaH, (CH3) 3SiOK, (CH3) 3SiONa. 8. The method according to claim 7, characterized in that difluoro (trimethyl) silicon tris (diethylamino) sulfonate or tetrabutylammonium fluoride are used as activators. 9. The method according to claim 8, characterized in that tetrabutylammonium fluoride is used as activators. Process according to claim 1 or 2, 5 or 7, characterized in that the reaction is preferably carried out in a solvent selected from the group: dioxane, THF, diethyl ether, benzene, toluene, chlorobenzene, N-methylpyrrolidone, DMF, dimethoxyethane and their mixtures. 11. A method for the preparation of 1,3,5-tri (E) -styrylbenzenes of the general formula I, wherein: - R represents an atom: H, Cl or Br, characterized in that in the first step silylation coupling reactions are carried out between styrene or 4-halogenostyrene and 1,3-divinyl tetramethyldisiloxane in the presence of a silylating coupling catalyst in an organic solvent, optionally with the addition of a cocatalyst, followed by completion of the silylating coupling reaction, in the same reaction medium, a desilylating coupling reaction between the substituted 1,3-bis (styryl) tetramethyldisiloxane obtained in the first step and the corresponding trihalobenzene of the general formula 3, wherein - X represents iodine or bromine, where X may be three identical or different atoms, in the presence of a desilylating coupling catalyst and an activator in an organic solvent, the desilylating coupling reagents and optional addition of solvent are added after the completion of the first step. PL 210 895 B1 12. The method according to p. 11. The process of claim 11, wherein the silylation coupling catalyst is a compound selected from the group: RuHCl (CO) (PPh3) 3 complex, ([RuH (Cl) (CO) (PCy3) 2]), [RuCl2 (CO) 3] 2). 13. The method according to p. The process of claim 12, characterized in that RuHCl (CO) (PPh3) 3 is used as the catalyst, optionally with the addition of a cocatalyst. 14. The method according to p. The process of claim 13, wherein CuCl is used as the cocatalyst. 15. The method according to p. The process of claim 11, wherein the solvent is selected from the group: benzene, toluene, chlorobenzene, ether derivatives or a mixture thereof. 16. The method according to p. The process of claim 11, wherein the desilylating coupling catalyst is a compound selected from the group: palladium (0) complexes or palladium (II) and (IV) compounds. 17. The method according to p. 16. The process of claim 16, wherein the desilylating coupling catalyst is a compound selected from the group [Pd (PPh3) 4], [Pd (dba) 2], [Pd2 (dba) 3], [Pd2 (dba) 3] xCHCl3, PdCl2 , PdBr ₂ , Pd (CH ₃ COO) ₂ , Pd (OTf) ₂ , [PdCl (n ₃ -C ₃ H ₅ )] ₂ , [PdCl ₂ (PhCN) ₂ ], [PdCl ₂ (PPh ₃ ) ₂ ] ( COD) PdBr ₂ , [allylPdCl] 2, (PPh3) 2BnPdCl. 18. The method according to p. The process of claim 17, wherein the desilylating coupling catalyst is [Pd2 (dba) 3]. 19. The method according to p. The process of claim 16, wherein the desilylating coupling catalyst is palladium (0), (II) and (IV) compounds in the presence of a ligand selected from the group: phosphines, cyclic tertiary amines. 20. The method according to claim, characterized in that the ligands are a compound selected from the group: tris (2-methylphenyl) phosphorus, (P (o-tol) 3), Ph3PO, 1,4-diazabicyclo [2.2.2] octane, triphenylphosphine (PPh3). 21. The method according to claim 16, 17 or 19, characterized in that the activators are compounds selected from the group: fluoride salts, Cs2CO3, Ag2O, CuJ, K2CO3, NaOH, KOH, NaH, (CH3) 3SiOK, (CH3) 3SiONa. 22. The process according to claim 21, characterized in that difluoro (trimethyl) silicon tris (diethylamino) sulfonate or tetrabutylammonium fluoride are used as activators. 23. The method according to claim 22, characterized in that tetrabutylammonium fluoride is used as activators. 24. The process according to claim 16, 17, 19 or 22, characterized in that the reaction is preferably carried out in a solvent selected from the group: dioxane, THF, diethyl ether, benzene, toluene, chlorobenzene, N-methylpyrrolidone, DMF, dimethoxyethane and their mixtures.