PL220130B1 - New derivative of acetylene and the production method thereof - Google Patents

Description

Description of the invention

The subject of the invention is a new acetylene derivative and a method of its preparation. The derivative according to the invention can be advantageously used for the synthesis of molecular and macromolecular nanomaterials with properties predisposing them to use in organic electronics, for example as luminescent and / or conductive materials.

The prior art discloses symmetrical, disubstituted acetylene derivatives of the ArC CAr type, which include the derivative of the present invention, where the Ar group is an aryl group such as, for example, phenyl substituted phenyl, 2-thienyl, 3-thienyl, substituted 2, 2'-bitophen-5-yl [R. Rathore, C. L. Burns, I. A. Guzei: Synthesis and Isolation of Polytrityl Cations by Utilizing Hexaphenylbenzene and Tetraphenylmethane Scaffolds, J. Org. Chem., 69, 1524-1530, (2004); K. Park, G. Bae, J. Moon, J. Choe, K. Ho Song, S. Lee: Synthesis of symmetrical and unsymmetrical diarylalkynes from propiolic acid using palladium-catalyzed decarboxylative coupling, J. Org. Chem., 75, 6244-6251, (2010); P. Chuentragool, K. Vongnam, P. Rashatasakhon, M. Sukwattanasinitt, S. Wacharasindhu: Calcium carbide as a cost-effective starting material for symmetrical diarylethynes via Pd-catalyzed coupling reaction. Tetrahedron, 67,8177-8182, (2011)]. These compounds are of great importance in modern organic synthesis. Namely, they are the substrates for various types of cycloaddition reactions, especially 4 + 2, 3 + 2 and 2 + 2 + 2, which allows to obtain multisubstituted carbo- and heterocyclic compounds. It is difficult to imagine modern organic synthesis without ArC CAr type reagents. There are also known compounds in which the Ar substituents are 2,2'-bitiophen-5-yl groups, but additionally containing alkyl substituents, i.e. they are alkyl-2,2'-bitiophen-5-yl substituents [Y. Geng, A. Fechtenkoetter, K. Muellen: Star-like substituted hexaarylbenzenes: synthesis and mesomorphic properties, J. Mater. Chem., 11, 1634-1641, (2001)]. However, a derivative of the ArC CAr type, where the Ar group would be a 2,2'-bitiophen-5-yl substituent is not known so far.

Various methods of preparation of disubstituted aryl groups, symmetric (ArC CAr) and unsymmetrical (Ar C CAr) derivatives of acetylene have been described in the literature, including those in which the aryl groups were 2-thienyl, 3-thienyl or 5'-alkyl-2,2. '-bitiophen-5-yl. The aryl reagents were bromides or iodides and the acetylene fragment donors were: acetylene gas [M. Pal, NG Kundlu: An improved procedure for the Synthesis of substituted acetylenes from the reaction of acetylene gas with aryl iodides under palladium-copper catalysis, J. Chem. Soc., Perkin Trans 1, 449-451, (1995); P. Chuentragool, K. Vongnam, P. Rashatasakhon, M. Sukwattanasinitt, S. Wacharasindhu: Calcium carbide as a cost-effective starting material for symmetrical diarylethynes via Pd-catalyzed coupling reaction. Tetrahedron, 67, 8177-8182, (2011)], trimethylsilylacetylene [R. Rathore, CL Burns, IA Guzei: Synthesis and Isolation of Polytrityl Cations by Utilizing Hexaphenylbenzene and Tetraphenylmethane Scaffolds, J. Org. Chem., 69, 1524-1530, (2004); MJ Mio, C. Kopel, JB Braun, TL Gadzika, KL Hull, RG Brisbois, Ch. J. Markworth, PA Grieco: One-pot synthesis of symmetrical and unsymmetrical bisarylethynes by modification of the Sonogashira coupling reaction, Org. Lett., 4, 3199-3202, (2002)] or propanoic acid [K. Park, G. Bae, J. Moon, J. Choe, K. Ho Song, S. Lee: Synthesis of symmetrical andunsymmetrical diarylalkynes from propiolic acid using palladium-catalyzed decarboxylative coupling, J. Org. Chem., 75, 6244-6251, (2010)]. Catalytic systems consisted of palladium and copper compounds, and THF, DMF or MeCN were used as solvents. In the processes in which the reagent was acetylene, it was generated in situ from CaC ₂ and water [P. Chuentragool, K. Vongnam, P. Rashatasakhon, M. Sukwattanasinitt, S. Wacharasindhu: Calcium carbide as a cost-effective starting material for symmetrical diarylethynes via Pd-catalyzed coupling reaction. Tetrahedron, 67, 8177-8182, (2011); W. Zhang, H. Wu, Z. Liu, P. Zhong, L. Zhang, X. Huang, J. Cheng: The use of calcium carbide in one-pot synthesis of symmetric diaryl ethynes, Chem. Commun., 46, 4826-4828, (2006)] or the gas was passed through the reaction system [M. Pal, NG Kundlu: An improved procedure for the Synthesis of substituted acetylenes from the reaction of acetylene gas with aryl iodides under palladium-copper catalysis, J. Chem. Soc., Perkin Trans 1,449-451 (1995)].

The disadvantage of the known methods of obtaining symmetrical, disubstituted acetylene derivatives of the ArC CAr type is the use of toxic or difficult to evaporate or easily oxidizing solvents in the form of THF, DMF or MeCN. Moreover, the solubility of acetylene in these solvents is much lower than in solvents

Used in the process according to the invention, i.e. in ketones, especially acetone. Importantly, none of the known methods concerns the synthesis of the ArC CAr derivative, where the Ar group would be a 2,2'-bitiophen-5-yl substituent.

The aim of the invention was to eliminate or reduce the indicated disadvantages occurring in the known methods of synthesis of ArC CAr type derivatives and to develop an effective and easy to carry out method of obtaining a new acetylene derivative of the ArC CAr type, where Ar is a 2,2'-bitiophen-5-yl substituent.

The essence of the invention is a novel acetylene derivative in the form of 1,2-bis (2,2'-bitiophen-5-yl) acetylene of the formula 1.

The essence of the invention is also a method of obtaining a new acetylene derivative in the form of 1,2-bis (2,2'-bitiophen-5-yl) acetylene of formula 1, characterized in that in a single reactor or in a cascade of two to four , preferably three reactors, a solution containing 5-iodo-2,2'-bitiophene, [PdCl2 (tertiary phosphine) 2], CuI and trialkylamine, preferably triethylamine, is prepared in molar proportions of 100: 0.1: 0.1 respectively: 200 to 100: 10: 100: 1000, in a solvent in the form of an aliphatic or cyclic alkylCOalkyl ketone, preferably in acetone, in a ratio of 0.2 to 2, preferably ₃ dm ^{3 of} ketone per 1 mole of 5-iodo-2.2 ' -bitiophene, then gaseous, dry acetylene with a content of less than 100 ppm of H 2 O and an oxygen content of less than 10 ppm is passed through the thus prepared solution. As acetylene is passed through the prepared solution, the contents of each reactor are mixed intensively by means of a mechanical or magnetic stirrer. The acetylene flow rate through the solution in the reactor (s) is in the range of 1 to 10 mol / h, the acetylene purge time is in the range of 3 to 12 h, preferably 6 h, and the reaction temperature is maintained in the range of 20 to 30 ° C C. After the acetylene gas was passed through the solution, the volatile fractions were evaporated with a rotary vacuum evaporator and the solid residue was subjected to silica gel column chromatography using preferably a solid phase extraction technique. The pure product is eluted with a liquid saturated hydrocarbon or a mixture of liquid saturated hydrocarbons, preferably hexane. A pure product is obtained in the form of a yellow-colored solid, melting point ranging from 164-165 ° C, with a yield of 73 to 76%. Palladium from the catalytic system is recovered as tetrachloropalladane in a practical quantitative yield after termination of the chromatography.

Preferably, the [PdCl ₂ (tertiary phosphine) _2] used _{[PdCl2 (PPh3) 2].}

Preferably, the flow rate of acetylene through the solution, in the variant with a single reactor, is in the range from 2 to 4 mol / h.

Preferably, the acetylene flow rate through the solution, in the variant with a cascade of reactors, is in the range from 6 to 8 mol / h.

Preferably, a solution containing 5-iodo-2,2'-bitiophene, [PdCl ₂ (tertiary phosphine) ₂ ], CuI and trialkylamine is prepared in the reactor (s) under an argon atmosphere.

The reaction for the preparation of 1,2-bis (2,2'-bitiophen-5-yl) acetylene according to the invention is generally shown in Scheme 1, where R is alkyl, for example ethyl, and a is a palladium-copper catalyst system in the form [PdCl2 (tertiary phosphine] + Cul.

None of the known methods relates to the synthesis of a derivative of the ArC CAr type, where the Ar group would be a 2,2'-bitiophen-5-yl substituent. The indicated substituent is not one of the many aryl substituents that have a typical or predictable effect on the synthetic result, and is extremely important in view of the potential advantageous uses of 1,2-bis (2,2'-bitiophen-5-yl) acetylene obtained according to the present invention. Namely, it enables the polymerization of compounds in cases where at least two such substituents are present in the structure of the molecule and is much more advantageous than simple 2-thienyl or 3-thienyl, the use of which is known from the state of the art [including: Krompiec M., Krompiec S., Ignasiak H., Łapkowski M., Kuś P., Stanek Ł., Penczek R., Lis S., Staniński K., Sajewicz M., Gębarowska K .: Synthesis and electropolymerization of 3,5-dithienylpyridines, their complexes and N-methylpyridinium cations, Synth. Met. 158, 831 (2008); M. Krompiec, S. Krompiec, I. Grudzka, M. Filapek, Ł. Skórka, T. Flak, M. Łapkowski: A cross-linked conjugated metallopolymer comprised of bisaxially coordinated ruthenium tetra t-butyl phthalocyanine connected by quaterthiophene linkers, Electrochim . Acta, 2011, 56 (19), 6824-6830]. Advantage of 2,2'-bitiophen-5-yl substituent over simple 2-thienyl

PL 220 130 B1 and 3-thienyl consists in increasing the conductivity of the polymer, increasing the stability of both the monomer and the polymer, and the more favorable electrochromic properties of the polymer obtained from the monomer which contains bitienyl groups instead of thienyl groups.

The innovative use of a ketone, preferably acetone, as a solvent for the coupling of Arl with acetylene in the process according to the invention results in many advantages, the most important of which are the high solubility of acetylene in such solvents, the general availability and low cost of such solvents, especially acetone and its low toxicity.

The use of a cascade of reactors is advantageous over the variant with a single reactor, namely it allows a better use of the gaseous reactant, i.e. acetylene. In addition, it allows to increase the product yield, because it allows to obtain practically three times more of the final product per unit of time, without the need to use a reactor with a much larger volume, more difficult to operate and control, and more demanding when it comes to gas mixing and bubbling.

The method of producing 1,2-bis (2,2'-bitiophen-5-yl) acetylene according to the invention will be explained in more detail on the basis of the following examples.

P r z k ł a d 1

One-step synthesis of 1,2-bis (2,2'-bitiophen-5-yl) acetylene.

1,2-bis (2,2'-bitiophen-5-yl) acetylene was obtained by reacting 5-iodo-2,2'-bitiophene with acetylene gas, in the presence of triethylamine as a hydrogen iodide binding agent, in acetone solution, in the presence of a catalyst palladium-copper. An exemplary process was carried out in accordance with Scheme 1, where the R was ethyl and the [PdCl2 (PPh3) 2] + CuI catalyst system was used as a.

In a single reactor, a solution was prepared containing 0.1 mol of 5-iodo-2,2'-bitiophene, 0.001 mol [PdCl ₂ (PPh ₃ ) ₂ ], 0.01 mol of CuI and 0.22 mol of triethylamine, in 0.5 dm. ^{3 of} dry acetone, and then dry acetylene with a content of less than 100 ppm of H ₂ O and an oxygen content of less than 10 ppm was passed through the solution prepared in this way, while intensively stirring it with a mechanical stirrer. The acetylene flow rate through the solution was 2 to 4 mol / h, the acetylene flow time was 6 h, and the temperature of the reaction mixture was maintained at 20 to 30 ° C. After the acetylene gas was passed through, the volatile fractions were evaporated off with a rotary vacuum evaporator. The solid residue was subjected to silica gel column chromatography using a solid phase extraction technique. Pure product was eluted with hexane. 1,2-bis (2,2'-bitiophen-5-yl) acetylene was obtained in the form of a yellow solid with a melting point ranging from 164-165 ° C with a yield of 76%. Upon completion of the chromatography from the catalytic system, the palladium was recovered in the form of tetrachloropalladate in a practically quantitative yield.

P r z k ł a d 2

Preparation of 1,2-bis (2,2'-bitiophen-5-yl) acetylene in a three-reactor cascade system.

, 2-bis (2,2'-bitiophen-5-yl) acetylene was obtained by reacting 5-iodo-2,2'-bitiophene with acetylene gas, in the presence of triethylamine as a hydrogen iodide binding agent, in acetone solution, in the presence of a palladium catalyst -copper.

The process was carried out in three identical reactors, connected in series and forming a cascade. All three reactors were filled with identical containing solutions

0.1 mole of 5-iodo-2,2'-bitiofenu, 0.001 mol [PdCl2 (PPh3) 2], 0.01 mol of CuI and 0.22 mol triethyl amine ₃ in 0.5 dm ³ of dry acetone. Dry acetylene gas with less than 100 ppm H 2 O and less than 10 ppm oxygen was passed through the solution filling the first reactor in the cascade. After leaving the first reactor, acetylene was fed to the second reactor, and after it was passed through to the third reactor. The acetylene flow rate through the solution ranged from 3 to 5 mol / h, the acetylene flow time was 6 h, and the temperature of the reaction mixture was maintained in the range of 20 to 30 ° C, and while acetylene was passed through the solution, it was intensively stirred with a mechanical stirrer. After passing acetylene through the cascade of reactors, the post-reaction mixtures from all three reactors in the cascade were combined and volatile fractions were evaporated using a vacuum rotary evaporator. The solid residue was subjected to silica gel column chromatography using a solid phase extraction technique. Pure product was eluted with hexane. 1,2-bis (2,2'-bitiophen-5-yl) acetylene was obtained in the form of a yellow solid with a melting point of

PL 220 130 B1 in the range from 164-165 ° C, with an efficiency of 76%. Upon completion of the chromatography from the catalytic system, the palladium was recovered in the form of tetrachloropalladate in a practically quantitative yield.

P r z k ł a d 3

Preparation of 1,2-bis (2,2'-bitiophen-5-yl) acetylene in a three-reactor cascade system.

1,2-bis (2,2'-bitiophen-5-yl) acetylene was obtained by reacting 5-iodo-2,2'-bitiophene with acetylene gas in the presence of tripropylamine as a hydrogen iodide binding agent in 2-butanone solution, the presence of a palladium-copper catalyst.

The process was carried out in three identical reactors, connected in series and forming a cascade. All three reactors were filled with identical solutions containing 0.1 mol of 5-iodo-2,2'-bitiophene, 0.001 mol [PdCl ₂ (PPh ₃ ) ₂ ], 0.01 mol of CuI and 0.22 mol of tripropylamine, in 0.5 dm ^{3 of} dry 2-butanone. Gaseous, dry acetylene with a content of less than 100 ppm H ₂ O and an oxygen content of less than 10 ppm was passed through the solution filling the first reactor in the cascade. After leaving the first reactor, acetylene was fed to the second reactor, and after it had passed through this reactor to the third reactor. The acetylene flow rate through the solution ranged from 3 to 5 mol / h, the acetylene flow time was 6 h, and the temperature of the reaction mixture was maintained in the range of 20 to 30 ° C, and while acetylene was passed through the solution, it was intensively stirred with a mechanical stirrer. After passing acetylene through the cascade of reactors, the post-reaction mixtures from all three reactors in the cascade were combined and volatile fractions were evaporated using a vacuum rotary evaporator. The solid residue was subjected to silica gel column chromatography using a solid phase extraction technique. Pure product was eluted with petroleum ether. 1,2-bis (2,2'-bitiophen-5-yl) acetylene was obtained in the form of a yellow solid with a melting point ranging from 164-165 ° C, a yield of 75%. Upon completion of the chromatography from the catalytic system, the palladium was recovered in the form of tetrachloropalladate in a practically quantitative yield.

The compound obtained by the method of the present invention can be advantageously used for the synthesis of molecular and macromolecular nanomaterials with properties predisposing them to use in organic electronics, for example as luminescent and / or conductive materials.

For example, in the polymerization of 1,2-bis (2,2'-bitiophen-5-yl) acetylene, poly-1,2-bis (2,2'-bitiophen-5-yl) acetylene was obtained, as illustrated in Scheme 2. which shows the build-up of a durable conductive polymer film.

The polymerization was carried out electrochemically, as shown in the voltamogram 1 and diagram 1.

Voltamogram 1. Preparation of polymer from 1,2-bis (2,2'-bitiophen-5-yl) acetylene

PL 220 130 B1

Graph 1. Graphical record of spectroelectrochemistry of a polymer film deposited on ITO (p-doping process).

Conducting polymer poly-1,2-bis (2,2'-bitiophen-5-yl) acetylene was obtained from 1,2-bis (2,2'-bitiophen-5-yl) acetylene under cyclic voltammetry in solution in CH2Cl2 (using 0.1 M BU4NPF6 as the auxiliary electrolyte). The polymerization was carried out in a three-electrode system, with a platinum working electrode, with an upper recycling potential equal to 0.7 V (relative to ferrocene), the record of this process is shown in the voltamogram 1. The use of the compound constituting the essence of the present invention in the synthesis of poly-1,2-bis ( 2,2'-bitiophen-5-yl) acetylene influenced the favorable properties of the latter. The obtained polymer is stable both during multiple p and n doping (Graph 1). It has been shown that the polymerization process takes place both without and in the presence of boron trifluoride and in the presence of some metal complexes, for example ruthenium. The obtained polymer is stable, conductive and exhibits electrochromism. It can be used as an organic semiconductor.

Claims (6)

Patent claims 1. A new acetylene derivative, which is 1,2-bis (2,2'-bitiophen-5-yl) acetylene of the formula 1. 2. The method of obtaining a new acetylene derivative, which is 1,2-bis (2,2'-bitiophen-5-yl) -acetylene of formula 1, characterized in that two to four connected in series in a single reactor or in a cascade, preferably three reactors, a solution is prepared containing 5-iodo-2,2'-bitiophene, [PdCl ₂ (tertiary phosphine) ₂ ], CuI and a trialkylamine, preferably triethylamine, in molar proportions of 100: 0.1: 0.1 respectively: 200 to 100: 10: 100: 1000, in a solvent in the form of an aliphatic or cyclic ketone type alkilCOalkil, wheel ₃ preferably in acetone, in proportions of 0.2 to 2, preferably 1 dm ³ per 1 mole of the ketone 5-iodo-2,2'-bitiofenu, followed by The solution prepared in this way is passed through gaseous, dry acetylene, content below 100 ppm H ₂ O and oxygen content below 10 ppm, while intensively stirring the content of each reactor using a mechanical or magnetic stirrer, the flow rate of acetylene through the solution in the reactor (s) is within the range from 1 to 10 mol / h, the acetylene flow time is in the range from 3 to 12 h, preferably 6 h, while the reaction temperature is kept in the range of 20 to 30 ° C, then, after the acetylene has been passed through the solution, volatile the fractions are carried out using a rotary vacuum evaporator and the solid residue is subjected to silica gel column chromatography using preferably a solid phase extraction technique, followed by The pure product in the form of a solid is eluted with a liquid saturated hydrocarbon or a mixture of liquid saturated hydrocarbons, preferably hexane. PL 220 130 B1 3. The method according to p. The process of claim 2, wherein [PdCl2 (tertiary phosphine) 2] is [PdCl2 (PPh3) 2]. 4. The method according to p. The process of claim 2, characterized in that the flow rate of acetylene through the solution, in the variant with a single reactor, ranges from 2 to 4 mol / h. 5. The method according to p. The process according to claim 2, characterized in that the acetylene flow rate through the solution, in the variant with a cascade of reactors, is in the range from 6 to 8 mol / h. 6. The method according to p. The process of claim 2, wherein the solution containing 5-iodo-2,2'-bitiophene, [PdCl ₂ (tertiary phosphine) ₂ ], CuI and trialkylamine is prepared in a reactor (s) under an argon atmosphere.