PL210894B1 - New symetric substituted 1,2,4,5-tetra(E)-styrilo benzenes and the method of obtaining of the substituted 1,2,4,5-tetra(E)-styrilo benzenes - Google Patents

Description

(12) PATENT DESCRIPTION (19) PL (11) 210894 (13) B1 (21) Application number: 386072 ^{(51) Int.Cl.}

C07C 15/52 (2006.01) (22) Date of filing: 12/09/2008

New symmetrically substituted 1,2,4,5-tetra (E) -styrylbenzenes and the method of preparation of substituted 1,2,4,5-tetra (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 210 894 B1

Description of the invention

The subject of the invention is new symmetrically substituted 1,2,4,5-tetra (E) -styrylbenzenes of the general formula 1 and a new method of synthesizing new and known symmetrically substituted 1,2,4,5-tetra (E) -styrylbenzenes of the general formula 1.

The symmetrically substituted 1,2,4,5-tetra (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 1,2,4,5-tetra (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 substituted 1,2,4,5-tetra (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 1,2,4,5-tetra (E) -styrylbenzene in the reaction between 1,2,4,5-tetramethylbenzene and benzylideneaniline in the presence of potassium tert-butoxide or potassium hydroxide in DMF in DMF. 90-95 ° C. This reaction is characterized by a very low yield of 2-3% of the E isomer.

The literature discloses (2) a method using the so-called Grignard reaction, the synthesis of 1,2,4,5-tetra (E) -styrylbenzene by reacting 1,2,4,5-tetrabromo-3,6-dichlorobenzene with phenylmagnesium bromide in THF. The reaction took 10-12 hours at room temperature. This reaction is characterized by a low efficiency of 49-65%.

From the literature (3), there is known a method for the preparation of 1,2,4,5-tetra (E) -styrylbenzene, consisting in the first stage of bromination of 1,2,4,5-tetramethylbenzene, and then the reaction of the thus obtained 1,2 , 4,5-tetrakis (bromomethyl) benzene in the so-called Michael-Arbuzov reaction with triethyl phosphite. The thus obtained tetraphosphonic ester is reacted by a Homer-Wadsworth-Emmons reaction with benzaldehyde in the presence of sodium methoxide to give 1,2,4,5-tetra (E) -styrylbenzene in a total yield of 29%.

The aim of the invention was to develop new symmetrically substituted 1,2,4,5-tetra (E) -styrylbenzenes and a cheap and efficient method of obtaining the known and new symmetrically substituted 1,2,4,5-tetra (E) -styrylbenzenes.

The present invention relates to new substituted 1,2,4,5-tetra (E) -styrylbenzenes of the general formula I, in which

- R is: Cl or Br,

In a second aspect, the invention relates to a process for synthesizing compounds of general formula 1, wherein:

- R is: H; Cl; Br

A desilylating coupling reaction, in the presence of a desilylating coupling catalyst and an activator, of a suitable substituted 1,3-bis (styryl) tetramethyldisiloxane of the general formula 2,

wherein R is H, Cl or Br, wherein R may be two identical or different atoms, with a suitable tetrahalobenzene of general formula 3, wherein

- X is iodine or bromine, where X may be four identical 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 a desilylating coupling catalyst system in the presence of an appropriate 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 palladium compounds.

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 about 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 preferred to use at least a 2.5-fold molar excess of 1,3-bis (styryl) tetramethyldisiloxane over tetrahalobenzene. 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.

PL 210 894 B1

When 1,3-bis ((E) -4-bromostyryl) tetramethyldisiloxane is used, the efficiency of the process is strongly related to the temperature, because as the temperature increases, the speed of competing polymerization reactions increases rapidly, which affects the efficiency of the process as well as complicates the purification processes of the final product, such as is the appropriately substituted 1,2,4,5-tetra (E) -styrylbenzene. Depending on the type of substrate used, it is advantageous to use the following temperatures:

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

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

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

- tetrabromobenzene 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 • 0.4 mol of the corresponding tetrahalobenzene • 2.4 mol of TBAF • 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 process according to the invention for the synthesis of substituted 1,2,4,5-tetra (E) -styrylbenzenes of the general formula I, in which R has the meaning given above, is a method that involves the use of a sequence (so-called "one-pot reaction"). ") Two reactions: the silylating coupling of styrene or 4-halostyrene with 1,3-divinyl tetramethyldisiloxane, followed by the desilylating coupling of the substituted 1,3-bis (styryl) tetramethyldisiloxane formed in the first step with tetrahalobenzene of general formula 3, where R is above given meaning.

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 (Cl) (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 speed and efficiency. In the case of using RuHCl (CO) (PPh3) 3, the addition of CuCl as a cocatalyst has a beneficial effect 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.

PL 210 894 B1

The silylating coupling reaction is carried out in solvents having 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).

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 exceeds 99%. .

In the reaction, according to the process of the invention, an excess of styrene or 4-halogenostyrene is used compared 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 approx. 4-fold excess. 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-divinylteramethylsiloxane above 99% cannot be achieved due to e.g. uncontrolled loss of styrene or 4-halostyrene, 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 tetrahalobenzene 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 completion of the first stage, the appropriate tetrahalobenzene of the general formula III, 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 complete dissolution of the substrates, 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 tetrahalobenzene 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. An activator and a sufficient amount of solvent are added to the reaction mixture obtained after the first step, so that the starting materials are completely

Then the catalyst is added and after heating to a temperature of approx. 30 ° C, the reaction is carried out with stirring until maximum conversion is obtained.

The process according to the invention enables the preparation of 1,2,4,5-tetra (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, allows the process to be significantly simplified and the synthesis time of the substituted 1,2,4,5-tetra (E) -styrylbenzenes to be shortened, while only slightly reducing the final yields.

The synthesis of symmetric substituted 1,2,4,5-tetra (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 dioxane 0.116 g ( 0.2 mmol) 1,2,4,5-tetra-iodobenzene, 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 30 ° C for 24 h. The resulting precipitate of the product 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 previously filtered precipitate and dried in a vacuum. 0.075 g 1,2,4,5-tetra (E) -styrylbenzene was obtained, which is 77% of theory.

Yellow-green crystals; efficiency: 77%; mp = 262-266 ° C.

IR (KBr, cm ^-1 ): 3056.9, 3024.6, 2953.8, 2923.2, 1663.9, 1645.1, 1597.9, 1494.1, 1447.8, 1363.8, 1301.0, 1072.0, 1028.0, 959.8,814.9, 747.2, 692.1.

^1H NMR (C6D6): δ = 7.06-7.35 (m, 28 H, C6H5-CH = CH), 7.71 (s, 2 H, C6H2).

MS (EI): m / z (%) = 486 (3), 384 (84), 293 (82), 282 (100), 238 (48), 220 (54), 205 (60), 191 (60 ), 178 (83), 165 (58), 133 (67), 115 (59), 105 (63), 91 (99), 77 (66);

(El): m / z cal. for C38H28: 484.2191; found: 484.2173.

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 whole was heated for another 24 h. The progress of the reaction was monitored by GC and GCMS analyzes until the 1,3-divinyl tetramethyldisiloxane was completely converted (conversion above 99%). Then the mixture was cooled to room temperature, and after cooling it into the reaction vessel under argon, it was charged with: 3.0 ml of dioxane, 0.116 g (0.2 mmol) of 1,2,4,5-tetra-iodo-benzene, 0.32 g (1.2 mmol) of fluoride. tetrabutylammonium (TBAF), then 9.16 mg (0.01 mmol) of palladium complex [Pd2 (dba) 3] was added after the starting materials had dissolved. The system was placed back in the oil bath and, keeping the temperature at 30 ° C, left for 24 h. The resulting precipitate was filtered off, and the filtrate was loaded onto a column filled with silica gel. 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. 0.070 g of 1,2,4,5-tetra (E) -styrylbenzene was obtained, which is 72% of theory.

Yellow-green crystals; efficiency: 72%; t, t = 262-267 ° C.

IR (KBr, cm ^-1 ): 3056.9, 3024.6, 2953.8, 2923.2, 1663.9, 1645.1, 1597.9, 1494.1, 1447.8, 1363.8, 1301.0, 1072.0, 1028.0, 959.8, 814.9, 747.2, 692.1.

^1H NMR (C6D6): δ = 7.06-7.35 (m, 28 H, C6H5-CH = CH), 7.71 (s, 2 H, C6H2).

PL 210 894 B1

MS (EI): m / z (%) = 486 (3), 384 (84), 293 (82), 282 (100), 238 (48), 220 (54), 205 (60), 191 (60 ), 178 (83), 165 (58), 133 (67), 115 (59), 105 (63), 91 (99), 77 (66);

(El): m / z cal. for C38H28: 484.2191; found: 484.2173.

P r z k ł a d 3

Under the conditions as in example 2, a reaction in the first step was carried out between 0.1 g (0.5 mmol) of 1,3-divinyl tetramethyldisiloxane and 0.366 g (2.0 mmol) of 4-bromostyrene in the presence of 9.52 mg [RuHCl (CO) (PPh3) 3] and 2 ml of dioxane, and in the second step 0.116 g (0.2 mmol) of 1,2,4,5-tetra-iodobenzene, 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 30 ° C.

0.152 g 1,2,4,5-tetrakis ((E) -4-bromostyryl) benzene was obtained (yield: 95%); as a yellow powder, mp = 265-268 ° C.

Yellow powder; efficiency: 95%; mp = 265-268 ° C.

IR (KBr, cm ^-1 ): 798.9, 845.4, 956.6, 1008.5, 1072.1, 1258.5, 1487.9, 1587.4, 1682.4, 1725.1, 2924.1,2957.9,3049.3.

¹ H NMR (THF-d8): δ = 7.19 (d, J = 16.0 Hz, 4H, C6H2-CH =), 7.50-7.58 (m, 16 H, Br, C6H4), 7.67 (d, J = 16.1 Hz , 4 H, BrC6H4-CH =), 7.98 (s, 2H, C6H2),

MS (EI): m / z (%) = 802 (5), 633 (14), 308 (20), 196 (32), 185 (64), 91 (95), 57 (100);

Elemental analysis: comp. for C38H26Br4: C, 56.89; H, 3.27. Measured: C, 56.58; H, 3.03.

P r z k ł a d 4

Under the conditions as in example 2, a reaction in the first step was carried out between 0.1 g (0.5 mmol) of 1,3-divinyl tetramethyldisiloxane and 0.277 g (2.0 mmol) of 4-chlorostyrene in the presence of 9.52 mg [RuHCl (CO) (PPh3) 3] and 2 ml of dioxane, and in the second step 0.116 g (0.2 mmol) of 1,2,4,5-tetra-iodobenzene, 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 30 ° C.

0.097 g 1,2,4,5-tetrakis ((E) -4-chlorostyryl) benzene was obtained (yield: 78%); as a yellow powder, mp = 242-246 ° C.

Yellow powder; efficiency: 78%; mp = 242-246 ° C.

IR (KBr, cm ^-1 ): 808.2, 853.3, 960.3, 1012.2, 1091.7, 1492.4, 1592.4, 1667.7, 1686.8, 2924.6, 2955.8, 3027.2.

^1H NMR (C6D6): δ = 6.96 (d, J = 16.2 Hz, 4H, C6H2-CH =), 7.06-7.17 (m, 16 H, C6H4), 7.44 (d, J = 16.2 Hz, 4 H , ClC6H4-CH =), 7.87 (s, 2H, C6H2),

MS (EI): m / z (%) = 622 (6), 248 (32), 178 (51), 139 (68), 125 (100);

Elemental analysis: comp. for C38H26CI4: C, 73.09; H, 4.20. Measured: C, 72.81; H, 4.01.

Literature

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

2. Harada, K .; Hart, H .; Du, C-J.F. J. Org. Chem. 1985, 50, 5524

3. Muller, E .; Fritz, H.-G .; Munk, K .; Straub, H. Tetrahedron Lett 1969, 59, 5167.

Claims (25)

Patent claims 1. Novel substituted 1,2,4,5-tetra (E) -styrylbenzenes of general formula I in which - R is: Cl or Br, PL 210 894 B1 2. A method for the preparation of 1,2,4,5-tetra (E) -styrylbenzenes of the general formula I, in which: - R is: H, Cl; Br, characterized in that a desilylating coupling reaction is performed between an appropriately substituted 1,3-bis (styryl) tetramethyldisiloxane of the general formula II, in which Z is H, Cl or Br, where Z may be two identical or different atoms, and a suitable tetrahalobenzene of general formula 3 wherein - X is iodine or bromine, where X may be four identical or different atoms, in the presence of a desilylating coupling catalyst and an activator in an organic solvent under an inert gas atmosphere. 3. The method according to p. The process of claim 2, wherein the desilylating coupling catalyst is a compound selected from the group: palladium (0) complexes or palladium (II) and (IV) compounds. 4. The method according to p. 3. The process of claim 3, 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 , PdBr2, 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. 5. The method according to p. The process of claim 4, wherein [Pd2 (dba) 3] is used as the desilylating coupling catalyst. 6. The method according to p. The process of claim 2, 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. 7. The method according to p. 4. The process according to claim 4, 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 ). The method according to claim 2, 3 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 . 9. The process according to claim 8, characterized in that difluoro (trimethyl) silicon tris (diethylamino) sulfonate or tetrabutylammonium fluoride are used as activators. 10. The method according to claim 9, characterized in that tetrabutylammonium fluoride is used as activators. 11. The process according to claim 2 or 3, 6 or 8, 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. PL 210 894 B1 12. A method for the preparation of 1,2,4,5-tetra (E) -styrylbenzenes of the general formula 1, (1) in which: -R is: H, Cl; Br, characterized in that in the first step, silylating coupling reactions are carried out between styrene or 4-halostyrene and 1,3-divinyl tetramethyldisiloxane, in the presence of a silylating coupling catalyst in an organic solvent, optionally with the addition of a cocatalyst, and then, after completion of the silylating coupling reaction, in in the same reaction medium, in the second step a desilylating coupling reaction is carried out between the substituted 1,3-bis (styryl) tetramethyldisiloxane obtained in the first step and the corresponding tetrahalobenzene of the general formula 3, in which (3) - X represents iodine or bromine, where X may be four 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. 13. The method according to p. 12. The process of claim 12, 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) 14. The method according to p. A process as claimed in claim 13, characterized in that RuHCl (CO) (PPh3) 3 is used as catalyst, optionally with the addition of a cocatalyst. 15. The method according to p. The process of claim 14, wherein CuCl is used as the cocatalyst. 16. The method according to p. The process of claim 12, wherein the solvent is selected from the group: benzene, toluene, chlorobenzene, ether derivatives or a mixture thereof. 17. The method according to p. The process of claim 12, wherein the desilylating coupling catalyst is a compound selected from the group: palladium (0) complexes or palladium (II) and (IV) compounds. 18. The method according to p. 17, characterized in that 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 , [PdCI (n ₃ -C ₃ H ₅ )] ₂ , [PdCl ₂ (PhCN) ₂ ], [PdCl ₂ (PPh ₃ ) ₂ ] (COD) PdBr ₂ , [allylPdCI] 2, (PPh3) 2BnPdCI. 19. The method according to p. The process of claim 18, wherein the desilylating coupling catalyst is [Pd2 (dba) 3]. 20. The method according to p. The process of claim 17, 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. 21. The method according to p. 20, 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 ). 22. The method according to claim 17, 18 or 20, characterized in that the activators are compounds selected from the group: fluoride salts, Cs2CO3, Ag2O, CuJ, K2CO3, NaOH, KOH, NaH, (CH3) 3SiOK, (CH3) 3SiONa. 23. The process according to claim 22, characterized in that difluoro (trimethyl) silicon tris (diethylamino) sulfonate or tetrabutylammonium fluoride are used as activators. PL 210 894 B1 24. The method according to claim 23, characterized in that tetrabutylammonium fluoride is used as activators. 25. The process according to claim 17 or 18 or 20 or 23, characterized in that the reaction is preferably carried out in a solvent selected from the group: dioxane, THF, diethyl ether, benzene, Publishing Department of the Polish Patent Office