WO2011087130A1

WO2011087130A1 - Acetylene compound and organic semiconductor material comprising same

Info

Publication number: WO2011087130A1
Application number: PCT/JP2011/050749
Authority: WO
Inventors: 純蔵大寺; 明浩折田; 尚杉岡; 浩一金平
Original assignee: 株式会社クラレ
Priority date: 2010-01-18
Filing date: 2011-01-18
Publication date: 2011-07-21
Also published as: JPWO2011087130A1

Abstract

Provided is an acetylene compound, the molecule of which has been designed so as to have planarity and symmetricity whereby π electrons can be widely delocalized. The acetylene compound serves as an organic semiconductor material in which electrons move smoothly and which exhibits strong N-type characteristics. Also provided is an N-type organic semiconductor material comprising the acetylene compound. The acetylene compound is a compound represented by chemical formula (I), wherein at least four of R¹ to R¹⁶, X¹, and X² are the same as or different from one another and represent linear, branched, and/or cyclic C_1-20 perfluoroalkyl groups or fluorine atoms, and the remainder are the same as or different from one another and represent linear, branched, and/or cyclic C_1-20 hydrocarbon groups or hydrogen atoms.

Description

Acetylene compound and organic semiconductor material containing the same

The present invention relates to an acetylene compound that is useful as a semiconductor material exhibiting N-type characteristics of an organic electronic device, and an N-type organic semiconductor material containing the acetylene compound.

Π-conjugated organic compounds generally have semiconducting properties and are called organic semiconductors. In recent years, organic electronic devices such as organic thin film transistors, organic electroluminescence, printable circuits, organic capacitors, and organic solar cells have attracted attention, and much research has been conducted on the development of organic semiconductor materials.

For example, Patent Document 1 discloses an aryl group-containing triamine compound useful as a hole transport material or a light emitting material for an organic electroluminescence device and a method for producing the same. Patent Document 2 discloses an organic electroluminescent device containing an aromatic amine compound having a triazine skeleton in a hole transport layer.

Organic semiconductor materials are roughly classified into P-type semiconductors related to hole injection or hole transport and N-type semiconductors related to electron injection or electron transport. At present, a large number of P-type organic semiconductor materials have been reported regardless of whether they are small molecules or polymers, but N-type organic semiconductor materials are rarely reported. This generally has the problem that an N-type organic semiconductor has a characteristic of easily attracting electrons from the outside, is easily oxidized by oxygen in the air, easily loses its original N-type characteristic, and does not exist stably. It is because it is doing. In particular, the stronger the electron withdrawing ability, the greater the tendency to oxidize, so it has been said that the development of materials having strong N-type organic semiconductor characteristics is relatively difficult compared to P-type materials.

Examples of reported N-type organic semiconductors include fluorine substitution of π-conjugated compounds such as pentacenes (Non-Patent Document 1), oligothiophenes (Non-Patent Document 2), and copper phthalocyanine compounds (Non-Patent Document 3), and fullerenes. A derivative (nonpatent literature 4) is mentioned. These N-type organic semiconductors, pentacenes, and the like can delocalize π electrons widely, but by themselves, the movement of electrons in device electrodes and organic semiconductors, and the movement of electrons between organic semiconductors are insufficient. Is. A fullerene derivative is a typical N-type organic semiconductor, but a fullerene skeleton requires a special manufacturing method such as arc discharge or plasma decomposition, and is therefore expensive and difficult to say as an industrially suitable material. As described above, proposals for N-type organic semiconductors have been made energetically, but further proposals for new organic semiconductor compounds are indispensable for improving the performance of various devices.

On the other hand, as shown in Non-Patent Document 5, the present inventors have reported arylene ethynylene derivatives, all of which have the properties of P-type semiconductors and N-type. The compound which shows the property is not known.

JP-A-11-292860 JP-A-11-354284

The present invention has been made in order to solve the above problems, and has a molecular design having planarity and symmetry so that π electrons can be widely delocalized. It aims at providing the acetylene compound used as the organic-semiconductor material which shows, and the N type organic-semiconductor material containing it.

The acetylene compound according to claim 1 made to achieve the above object has the following chemical formula (I):

(In the formula, at least four of R ¹ to R ¹⁶ , X ¹ and X ² are the same or different from each other, and are linear, branched and / or cyclic perfluoroalkyl groups having 1 to 20 carbon atoms. Or a fluorine atom, and the remainder is a linear, branched and / or cyclic hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom which may be the same or different from each other and may have a substituent. It is represented by.

The acetylene compound according to claim 2 is the one described in claim 1, wherein X ¹ and X ² are the same or different perfluoroalkyl groups, and R ¹ to R ¹⁶ are , At least four of which are fluorine atoms.

The N-type organic semiconductor material according to claim 3 contains the acetylene compound according to claim 1.

The acetylene compound of the present invention has a fluorine atom or a perfluoroalkyl group introduced into a planar arylene ethynylene skeleton, and can be an organic semiconductor material exhibiting strong N-type characteristics.

The N-type organic semiconductor material of the present invention can realize efficient electron transfer between a device electrode and an organic semiconductor and smooth electron transfer between organic semiconductor molecules.

Hereinafter, preferred modes for carrying out the present invention will be described in detail, but the scope of the present invention is not limited to these modes.

The acetylene compound of the present invention is represented by the chemical formula (I), and has a fluorine atom or a perfluoroalkyl group introduced into the arylene ethynylene skeleton. In addition, this acetylene compound has a molecular design with planarity and symmetry that allows π electrons to be widely delocalized, and when used as an organic semiconductor material, its lowest unoccupied orbital (LUMO) level and device This shows a good balance with the work function of the electrode.

In the chemical formula (I), the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent represented by R ¹ to R ¹⁶ , X ¹ and X ² may have a substituent, for example. Examples thereof include an alkyl group, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and an aryl group which may have a substituent.

The alkyl group may be a linear or branched alkyl group or a cyclic alkyl group. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, isohexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group and other linear or branched alkyl groups; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptanyl group, cyclooctanyl group And cycloalkyl groups such as cyclononanyl group, cyclodecanyl group, cycloundecanyl group, and cyclododecanyl group.

The alkyl group may have a substituent. Examples of the substituent include an aryl group such as a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group; a pyridyl group, a thienyl group, a furyl group, a pyrrolyl group, Heteroaromatic groups such as imidazolyl, pyrazinyl, oxazolyl, thiazolyl, pyrazolyl, benzothiazolyl, benzoimidazolyl; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy , Alkoxy groups such as tert-butoxy group, pentyloxy group, isopentyloxy group, neopentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group; Methylthio group Alkylthio groups such as ethylthio group, propylthio group and butylthio group; arylthio groups such as phenylthio group and naphthylthio group; trisubstituted silyloxy groups such as tert-butyldimethylsilyloxy group and tert-butyldiphenylsilyloxy group; methylsulfinyl group and ethyl Alkylsulfinyl groups such as sulfinyl groups; arylsulfinyl groups such as phenylsulfinyl groups; sulfonic acid ester groups such as methylsulfonyloxy groups, ethylsulfonyloxy groups, phenylsulfonyloxy groups, methoxysulfonyl groups, ethoxysulfonyl groups, and phenyloxysulfonyl groups Cyano group; nitro group; and the like.

The alkenyl group may be linear, branched or cyclic. Examples of the alkenyl group include a vinyl group, an allyl group, a methylvinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.

The alkynyl group may be linear or branched. Examples of the alkynyl group include ethynyl group, propynyl group, propargyl group, butynyl group, pentynyl group, hexynyl group, and phenylethynyl group.

These alkenyl groups and alkynyl groups may have a substituent, and the same substituents as those exemplified for the alkyl group can be used as such substituents.

Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. These aryl groups may have a substituent, and as such a substituent, a substituent other than the aryl group exemplified for the alkyl group, the above-described alkyl group, alkenyl group, alkynyl group, and the like can be used.

In the chemical formula (I), the perfluoroalkyl group represented by R ¹ to R ¹⁶ , X ¹ and X ² is, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec- A butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, isohexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, etc. Chain or branched chain alkyl groups; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptanyl group, cyclooctanyl group, cyclononanyl group, cyclodecanyl group, cycloundecanyl group, cyclododecanyl group, etc. Straight chain, branched chain or cyclic, such as 1 to 20 carbon atoms Of the hydrogen atoms of the kill group, in which 80-100% is substituted with a fluorine atom. The perfluoroalkyl group in the present invention includes a partial fluoroalkyl group in which the fluorine atom is 80% or more and less than 100% of the number of hydrogen atoms of the alkyl group.

In the acetylene compound of the present invention, at least four of R ¹ to R ¹⁶ , X ¹ and X ² are perfluoroalkyl groups or fluorine atoms, and examples thereof include the following compounds (1) to (14). Among these, a perfluoroalkyl group or a group having 8 or more fluorine atoms is more preferable. Further, these R ¹ to R ¹⁶ , X ¹ and X ² may be the same or different.

These acetylene compounds can be obtained by a method based on the so-called Sonogashira cross-coupling reaction between the corresponding phenyl halide compound and the phenylacetylene compound, a method of reacting an aromatic fluorine compound with a phenylacetylide compound, or a combination thereof. Can be synthesized by different methods.

One synthesis example of the acetylene compound of the present invention is shown below.

Synthesis of an acetylene compound in which, in the chemical formula (I), R ⁵ to R ¹² are all fluorine atoms, R ¹³ to R ¹⁶ are the same as R ¹ to R ^4, and X ² is the same as X ¹ An example is shown in chemical reaction formula (II) below.

In the chemical reaction formula (II), Z of the terminal alkyne compound to be reacted with the phenyl halide compound is a hydrogen atom or an alkylsilane (—SiR ′ ₃ ). The alkylsilane (—SiR ′ ₃ ) is preferably such that R ′ is lower alkyl such as methyl or ethyl.

The phenylacetylene compound constituting a part of the acetylene compound by the Sonogashira cross-coupling reaction between the phenyl halide compound and the terminal alkyne compound (ZC≡C—H) in the step (A) of the chemical reaction formula (II) Get. Subsequently, the phenylacetylene compound constituting a part of the acetylene compound (I) obtained in the step (A) is desorbed by the action of a base to acetylate (B-1) to obtain a phenylacetylide anion. The desired acetylene compound is synthesized by reacting (B-2) with perfluorodiphenylacetylene, which is an aromatic fluorine compound.

In addition, although the example in which the halogen substituent of the phenyl halide compound is an iodine atom has been shown, the halogen substituent may be a bromine atom or a chlorine atom.

In the chemical reaction formula (II), the Sonogashira cross-coupling reaction in the step (A) is preferably performed in the presence of a palladium catalyst, a copper catalyst and a base.

In the step (B) of reacting the phenyl acetylide compound obtained in the step (A) with an aromatic fluorine compound, the acetylation (B-1) is preferably performed in the presence of a solvent and a base. Furthermore, the reaction (B-2) of the phenylacetylene compound that constitutes a part of the acetylene compound and perfluorodiphenylacetylene is preferably carried out in the presence of a solvent.

Examples of the base used include, when Z is a hydrogen atom, organolithium compounds such as n-butyllithium, s-butyllithium and t-butyllithium; metal hydrides such as sodium hydride and potassium hydride; Metal hydroxides such as sodium and potassium hydroxide; and Grignard compounds such as methylmagnesium bromide, ethylmagnesium chloride, and phenylmagnesium chloride. When Z is alkylsilane (—SiR ′ ₃ ), tetraethylammonium fluoride, Examples thereof include ammonium fluoride such as tetrabutylammonium fluoride.

The solvent used is preferably a solvent that can be used even in the presence of a base, in which each compound as a raw material is dissolved to such an extent that the reaction rate is not hindered. Examples of such a solvent include tetrahydrofuran, diethyl ether, n-hexane, cyclohexane, n-heptane and the like.

The acetylene compound thus obtained can be isolated and purified by a method usually performed in the isolation and purification of organic compounds. For example, the reaction mixture is separated into an organic layer and an aqueous layer using a separatory funnel, and the aqueous layer is extracted with a solvent such as diethyl ether, ethyl acetate, toluene, methylene chloride, 1,2-dichloroethane, and the extract. The organic layer is combined, dried over anhydrous sodium sulfate, etc., and then concentrated, and the crude product obtained by concentration is purified by sublimation, recrystallization, distillation, silica gel column chromatography, etc. An acetylene compound can be obtained.

Examples 1 to 5 show the synthesis of acetylene compounds to which the present invention is applied.

Example 1
A chemical reaction formula (III) for obtaining 2,3,4,5,6-pentafluorodiphenylacetylene (a) as an intermediate compound for synthesizing the acetylene compound is shown below.

To a reactor substituted with nitrogen, tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ) (0.10 mmol, 0.12 g), copper (I) iodide (0.10 mmol, 19 mg), pentafluoroiodo Benzene (2.0 mmol, 0.59 g) was added and dissolved in toluene (10 ml) and diisopropylamine (1 ml). After phenylacetylene (2.4 mmol, 0.26 ml) was added, the mixture was stirred at room temperature for 15 hours. The reaction mixture was washed 3 times with a saturated aqueous ammonium chloride solution and then extracted 3 times with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over sodium sulfate, concentrated and dried under reduced pressure. Then, the intermediate compound (a) was obtained as a white solid by purifying with silica gel column chromatography (developing solvent: hexane) (yield: 456 mg, yield: 85%).

¹ H and ¹⁹ F nuclear magnetic resonance (NMR) spectrum data of the intermediate compound (a) are shown below. Ar represents aryl.
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 7.36 to 7.43 (m, 3H, Ar), 7.57 to 7.61 (m, 2H, Ar)
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ: −162.45 to −162.27 (m, 2F, Ar), −153.28 (t, J = 20.6 Hz, 1F, Ar), −136. 62 to -136.52 (m, 2F, Ar)
These analytical data support the structure of the intermediate compound (a) represented by the chemical reaction formula (III).

A chemical reaction formula (IV) for synthesizing 4,4′-bis (phenylethynyl) -2,3,5,6-tetrafluorodiphenylacetylene (1) using the obtained intermediate compound (a) is shown below. .

4- (Phenylethynyl) phenylacetylene (0.82 mmol, 0.17 mg) was added to the reactor purged with nitrogen, and tetrahydrofuran (THF) (5 ml) was added. The mixture was cooled to −78 ° C., n-butyllithium (n-BuLi) (1.3757 M in hexane, 0.87 ml) was added, and the mixture was stirred at −78 ° C. for 15 minutes. Next, a solution of 2,3,4,5,6-pentafluorodiphenylacetylene (a) (0.68 mmol, 0.18 g) obtained in the above synthesis was added in THF (4 ml), and the mixture was warmed to room temperature and heated for 18 hours. Stir. Saturated aqueous ammonium chloride solution (20 ml) was added to the reaction mixture, and the mixture was extracted 3 times with dichloromethane (20 ml). After drying the organic layer with sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was purified by recrystallization using a mixed solvent of toluene and THF to obtain the desired product (1) as a yellow solid ( Yield: 180 mg, yield: 59%).

¹ H-NMR, ¹⁹ F-NMR, High-Resolution Mass Spectra of 4,4′-bis (phenylethynyl) -2,3,5,6-tetrafluorodiphenylacetylene (1), which is the target product The results of (HRMS)) are shown below.

HRMS uses a high performance double-focusing mass spectrometer JEOL-JMS700 (manufactured by JEOL Ltd.), acceleration voltage: 8 kV, ionization method: electron ionization method, ionization energy: 70 eV, detector voltage: 1.5 kV It was measured by. Moreover, it confirmed that it was an error range of 10 ppm or less with respect to the estimated composition of a target object.

¹ H-NMR (500 MHz, CDCl ₃ ) δ: 7.25 to 7.44 (m, 6H), 7.54 to 7.61 (m, 8H)
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ: −137.62 (s, 4F)
HRMS measured value: 450.0998 (calculated value: 450.1032)
These analytical data support the structure of the acetylene compound (1) represented by the chemical reaction formula (IV).

(Example 2)
A chemical reaction formula (V) for obtaining trimethylsilylethynylpentafluorobenzene (b) as an intermediate compound for synthesizing the acetylene compound is shown below. In the formula, TMS is an abbreviation for trimethylsilyl group (—Si (CH ₃ ) ₃ ).

A reactor purged with nitrogen was charged with Pd (PPh ₃ ) ₄ (0.25 mmol, 0.29 g), copper (I) iodide (0.25 mmol, 48 mg), pentafluorobromobenzene (5.0 mmol, 1.23 g). ) And dissolved in toluene (20 ml) and diisopropylamine (2 ml), trimethylsilylacetylene (5.5 mmol, 0.77 ml) was added, and the mixture was stirred at 80 ° C. for 15 hours. The reaction solution was washed 3 times with a saturated aqueous ammonium chloride solution and then extracted 3 times with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over sodium sulfate, filtered through filter paper, concentrated and dried under reduced pressure. Thereafter, the product was purified by silica gel column chromatography (developing solvent: hexane, Rf = 0.50). A colorless liquid in which 8% of a triynesilylacetylene diyne was mixed was obtained (yield 80%).
The ¹ H-NMR and ¹⁹ F-NMR spectral data of the colorless liquid are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.30 (s, 9H, TMS)
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ: −162.29 to −162.48 (m, 2F, Ar), −152.86 (t, J = 20.6 Hz, 1F, Ar), −136. 24 to -136.36 (m, 2F, Ar)
These analytical data support the structure of the intermediate compound (b) represented by the chemical reaction formula (V).

The chemical reaction formula (VI) for obtaining perfluorodiphenylacetylene (c) as an intermediate compound from the obtained intermediate compound (b) is shown below.

A reactor purged with nitrogen was charged with Pd (PPh ₃ ) ₄ (0.10 mmol, 0.12 g), copper (I) iodide (2.4 mmol, 0.24 g), pentafluoroiodobenzene (2.0 mmol, 0 .49 g) and dissolved in N, N-dimethylformamide (DMF) (4 ml) and diisopropylamine (0.40 ml), and then trimethylsilylethynylpentafluorobenzene (b) (2.4 mmol) obtained in the above synthesis was obtained. , 0.63 mg) was added and the mixture was heated and stirred at 80 ° C. for 15 hours. After cooling the reaction solution and adding 20 ml of ethyl acetate, the organic layer was washed three times with a saturated aqueous ammonium chloride solution. The aqueous layer was re-extracted 3 times with ethyl acetate, mixed with the previous organic layer, and dried over sodium sulfate. This solution was concentrated and evaporated under reduced pressure, and the resulting residue was subjected to silica gel column chromatography (developing solvent: hexane) and then recrystallized and purified with hexane to obtain intermediate compound (c) as a white solid ( Yield: 350 mg, yield: 49%).

The ¹⁹ F-NMR spectrum data of the intermediate compound (c) is shown below.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ: −161.08 to −161.28 (m, 2F, Ar), −149.89 (t, J = 20.6 Hz, 2F, Ar), −134. 84 to -134.94 (m, 2F, Ar)
These analytical data support the structure of the intermediate compound (c) represented by the chemical reaction formula (VI).

A chemical reaction formula (VII) for synthesizing 4,4′-bis (phenylethynyl) -perfluorodiphenylacetylene (7) using the obtained intermediate compound (c) is shown below.

To a reactor purged with nitrogen, phenylacetylene (0.62 mmol, 63 mg) and THF (1 ml) were added, then cooled to −78 ° C. and 2.1 equivalents of n-BuLi (1.3757 M in hexane solution). , 0.43 ml) was added and stirred for 30 minutes. To this mixture was added a THF (2.0 ml) solution of perfluorodiphenylacetylene (c) (0.28 mmol, 0.10 g) obtained in the above synthesis, and the mixture was warmed to room temperature and stirred for 15 hours. A saturated aqueous ammonium chloride solution (20 ml) was added to the reaction solution, and then extracted three times with dichloromethane (20 ml). The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, the obtained residue was subjected to gel filtration using a toluene solvent, and then recrystallized using THF to obtain the desired product (7). Obtained as a yellow solid (yield: 87.8 mg, yield: 60%).

The results of ¹ H-NMR, ¹⁹ F-NMR, and HRMS analysis of 4,4′-bis (phenylethynyl) -perfluorodiphenylacetylene (7), which is the target product, are shown below. HRMS was measured under the same conditions as in Example 1, and it was confirmed that the error range was 10 ppm or less with respect to the estimated composition of the target product.
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 7.41 to 7.43 (m, 3H, Ar), 7.61 to 7.63 (m, 2H, Ar)
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ: −136.86 to −136.71 (m, 2F, Ar), −136.25 to −136.11 (m, 2F, Ar)
HRMS measured value: 522.0702 (calculated value: 522.0655)
These analytical data support the structure of the acetylene compound (7) represented by the chemical reaction formula (VII).

(Example 3)
A chemical reaction formula (VIII) for obtaining 4-iodo-2,3,5,6-tetrafluorobenzotrifluoride (d) as an intermediate compound for synthesizing the acetylene compound is shown below.

A reactor purged with nitrogen was charged with iodine (1.0 mmol, 0.25 g), tetrafluorobenzotrifluoride (1.0 mmol, 0.22 g), tripotassium phosphate (2.0 mmol, 0.43 g) and THF. In addition, the mixture was stirred with heating at 130 ° C. for 2 hours. The reaction solution was cooled, washed once with a saturated aqueous sodium hydrogen sulfite solution (20 ml), the aqueous layer was re-extracted three times with diethyl ether (20 ml), and mixed with the previous organic layer. The organic layer was washed with saturated brine (20 ml) and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: hexane) to obtain an intermediate compound (d) (yield: 158 mg, yield: 46%).

The ¹⁹ F-NMR spectrum data of the intermediate compound (d) is shown below.
¹⁹ F-NMR (282 MHz, CD ₂ Cl ₂ ) δ: −138.27 to −137.88 (m, 2F, Ar), −116.85 to −116.69 (m, 2F, Ar), −55 .70 (t, J = 20.6 Hz, 3F, F ₃ C)
These analytical data support the structure of the intermediate compound (d) represented by the chemical reaction formula (VIII).

The chemical reaction formula (IX) for obtaining 4-trimethylsilylethynyl-2,3,5,6-tetrafluorobenzotrifluoride (e) as an intermediate compound from the obtained intermediate compound (d) is shown below.

A reactor substituted with nitrogen was charged with Pd (PPh ₃ ) ₄ (0.042 mmol, 48 mg), copper (I) iodide (0.042 mmol, 8 mg), and 4-iodo-2,3, obtained in the above synthesis. 5,6-Tetrafluorobenzotrifluoride (d) (0.73 mmol, 251 mg), toluene (4 ml) and diisopropylamine (0.4 ml) were added. Trimethylsilylacetylene (0.83 mmol, 0.11 ml) was added to the mixture, and the mixture was stirred with heating at 80 ° C. for 20 hours. The reaction mixture was cooled, washed with saturated aqueous ammonium chloride solution (20 ml) three times, and the aqueous layer was extracted three times with ethyl acetate (20 ml). The obtained organic layer was washed with saturated brine (20 ml) and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: hexane) to obtain a colorless liquid intermediate compound (e) (yield: 197 mg, yield: 86%).

The ¹ H-NMR and ¹⁹ F-NMR spectrum data of the intermediate compound (e) are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.30 (s, 9H, TMS)
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ: −141.59 to −141.22 (m, 2F, Ar), −134.90 to −134.76 (m, 2F, Ar), −56.78 (T, J = 21.0Hz, 3F, F ₃ C)
These analytical data support the structure of the intermediate compound (e) represented by the chemical reaction formula (IX).

Using the intermediate compound (e) obtained and the intermediate compound (c) obtained in Example 2, 4,4′-bis (2,3,5,6-tetrafluoro-4-trifluoromethylphenylethynyl Chemical reaction formula (X) for synthesizing) -perfluorodiphenylacetylene (14) is shown below.

In a reactor substituted with nitrogen, perfluorodiphenylacetylene (c) (0.28 mmol, 0.10 g) obtained in Example 2 and 4-trimethylsilylethynyl-2,3,5,6 obtained in the above synthesis were used. -Tetrafluorobenzotrifluoride (e) (0.67 mmol, 0.21 g) and THF (4 ml) were added and cooled to 0 ° C. Tetrabutylammonium fluoride (TBAF) (1.0 M tetrahydrofuran solution, 0.28 mmol, 0.028 ml) was added to the mixture and stirred at room temperature for 12 hours. A saturated aqueous ammonium chloride solution (20 ml) was added to the reaction solution, and then re-extracted three times with dichloromethane (20 ml). The solvent of the organic layer was distilled off under reduced pressure, gel filtration was performed using toluene, and then recrystallization purification was performed with toluene to obtain the target product (14) as a white solid (yield: 150 mg, yield: 67%).

¹⁹ F-NMR and HRMS analysis results of 4,4′-bis (2,3,5,6-tetrafluoro-4-trifluoromethylphenylethynyl) -perfluorodiphenylacetylene (14), which is the target product, are shown below. Shown in HRMS was measured under the same conditions as in Example 1, and it was confirmed that the error range was 10 ppm or less with respect to the estimated composition of the target product.
¹⁹ F-NMR (282 MHz, C ₆ D ₅ CD ₃ ) δ: −140.90 to −140.64 (m, 2F, Ar), −135.60 to −135.34 (m, 2F, Ar), −134.04 to −133.94 (m, 2F, Ar), −57.08 (t, J = 23.1 Hz, 3F, F ₃ C)
HRMS measured value: 801.9648 (calculated value: 801.9648)
These analytical data support the structure of the acetylene compound (14) represented by the chemical reaction formula (X).

Example 4
A chemical reaction formula (VI) for obtaining perfluorodiphenylacetylene (c), which is an intermediate compound for synthesizing the acetylene compound, using the intermediate compound (b) obtained in Example 2 is shown below.

Pd (PPh ₃ ) ₄ (0.10 mmol, 0.12 g), CuCl (2.4 mmol, 0.24 g), pentafluoroiodobenzene (2.0 mmol, 0.49 g) were added to the reactor substituted with nitrogen. , Dissolved in dry DMF (4 ml), diisopropylamine (0.40 ml). Trimethylsilylethynylpentafluorobenzene (b) (2.4 mmol, 0.63 mg) obtained in Example 2 was added, and the mixture was stirred at 80 ° C. for 15 hours. The reaction solution was washed 3 times with a saturated aqueous ammonium chloride solution and then extracted 3 times with ethyl acetate. The extract was dried over sodium sulfate, filtered through filter paper, concentrated and dried under reduced pressure. The product was purified by silica gel column chromatography (developing solvent: hexane, Rf = 0.43). Subsequently, recrystallization purification with hexane was performed to obtain the intermediate compound (c) as a white solid (yield 49%).

The chemical reaction formula (XI) for obtaining bis (2,3,5,6-tetrafluoro-4-aminophenyl) acetylene (f) as an intermediate compound from the obtained intermediate compound (c) is shown below.

Perfluorodiphenylacetylene (c) (2.0 mmol, 0.72 g) obtained by the above synthesis was added to a reactor substituted with nitrogen, and dissolved in THF (8 ml). After cooling to 0 ° C. and adding lithium hexamethyldisilazide (LiHMDS) (1.0 M tetrahydrofuran solution, 8.0 mmol, 8.0 ml), the mixture is warmed to room temperature and stirred for 18 hours. After quenching by adding aqueous ammonium chloride, extract three times with ethyl acetate. Concentration under reduced pressure yields an intermediate crude product. The crude product is added to a nitrogen purged reactor and dissolved with THF (5 ml). After cooling to 0 ° C. and adding TBAF (1.0 M tetrahydrofuran solution, 9.6 mmol, 9.6 ml), the mixture was stirred at room temperature for 15 hours. After stirring, water was added for quenching, followed by extraction with ethyl acetate three times. The extract was dried over sodium sulfate, filtered through filter paper, concentrated and dried under reduced pressure. Purification by silica gel column chromatography (developing solvent: ethyl acetate / hexane: 30, Rf = 0.26) gave the intermediate compound (f) as a white solid (yield 68%).

The ¹ H-NMR and ¹⁹ F-NMR spectrum data of the intermediate compound (f) are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 4.24 (s, 4H, NH ₂ )
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ: -162.46 to -162.64 (m, 4F, Ar), -138.89 to -139.04 (m, 4F, Ar)
These analytical data support the structure of the intermediate compound (f) represented by the chemical reaction formula (XI).

The chemical reaction formula (XII) for obtaining bis (2,3,5,6-tetrafluoro-4-iodophenyl) acetylene (g) as an intermediate compound from the intermediate compound (f) is shown below.

A reactor substituted with nitrogen was charged with bis (2,3,5,6-tetrafluoro-4-aminophenyl) acetylene (f) (2.0 mmol, 0.70 g) obtained in the above synthesis, I ₂ (12 mmol). , 3.0 g) was added and dissolved with CH ₃ CN (7.0 ml). At 30 ° C., t-butyl nitrite (t-BuONO) (8.0 mmol, 0.95 ml) was added dropwise and stirred for 4 hours. After completion of stirring, the mixture was washed once with an aqueous Na ₂ SO ₃ solution and then extracted three times with dichloromethane. The extract was dried over sodium sulfate, filtered through filter paper, concentrated and dried under reduced pressure. The product was purified by silica gel column chromatography (developing solvent: hexane, Rf = 0.30). Subsequently, recrystallization purification with hexane was performed to obtain the intermediate compound (g) as a white solid (yield 70%).

The ¹⁹ F-NMR spectrum data of the intermediate compound (g) is shown below.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ: −133.80 to −133.99 (m, 4F, Ar), −119.58 to −119.77 (m, 4F, Ar)
These analytical data support the structure of the intermediate compound (g) represented by the chemical reaction formula (VII).

1- (4-trimethylsilylethynyl-2,3,5,6-tetrafluorophenyl) -3,3,4,4,5,5,6,6,7, which is an intermediate compound for synthesizing acetylene compounds The chemical reaction formula (XIII) for obtaining 7,8,8,8-tridecafluorooctane (h) is shown below.

To the reactor purged with nitrogen, 2- (tridecafluorohexyl) ethyl iodide (1.2 mmol, 0.57 g) dissolved in diethyl ether (20 ml) was added and cooled to −78 ° C. T-BuLi (1.59 M n-pentane solution, 1.2 mmol, 0.75 ml) was added dropwise thereto, and the mixture was stirred for 30 minutes. Trimethylsilylethynylpentafluorobenzene (b) (1.0 mmol, 0.26 g) dissolved in diethyl ether (6.0 ml) was added dropwise, and the mixture was warmed to room temperature and stirred for 14 hours. Thereafter, quenched with aqueous _NH 4 Cl and extracted 3 times with ethyl acetate. The extract was dried over sodium sulfate, filtered through filter paper, concentrated and dried under reduced pressure. The product was purified by silica gel column chromatography (developing solvent: hexane, Rf = 0.53) to obtain the intermediate compound (h) as a white solid (yield 59%).

The ¹ H-NMR and ¹⁹ F-NMR spectrum data of the intermediate compound (h) are shown below. Is shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 2.30-2.47 (m, 2H, alkyl), δ: 3.06 (t, J = 7.68 Hz, 2H, alkyl)
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ: −145.06 to −145.24 (m, 2F, Ar), −137.007 to −137.25 (m, 2F, Ar), −126.61 To -126.78 (m, 2F, alkyl), -124.04 (s, 2F, alkyl), -123.44 (s, 2F, alkyl), -122.48 (s, 2F, alkyl),- 115.65 to −115.90 (m, 2F, alkyl), −81.34 (t, J = 9.59 Hz, 3F, alkyl)
These analytical data support the structure of the intermediate compound (h) represented by the chemical reaction formula (VIII).

From the intermediate compound (h), 1- (2,3,5,6-tetrafluorophenyl-4-ethynyl) -3,3,4,4,5,5,6,6,7, which becomes an intermediate compound The chemical reaction formula (VI) for obtaining 7,8,8,8-tridecafluorooctane (i) is shown below.

1- (4-Trimethylsilylethynyl-2,3,5,6-tetrafluorophenyl) -3,3,4,4,5,5,6,6,7,7,8,8,8- Tridecafluorooctane (h) (1.32 mmol, 0.78 g) is added, and CH ₂ Cl ₂ (4.0 ml) and methanol (4.0 ml) are added and dissolved. K ₂ CO ₃ (13.2 mmol, 1.82 g) was added, and the mixture was stirred for 30 minutes at 0 ° C. in a suspended state. Water was added to dissolve the K ₂ CO ₃ and extracted 3 times with CH ₂ Cl ₂ . Dry with sodium sulfate, filter with filter paper, concentrate and dry under reduced pressure. Purification by silica gel column chromatography (developing solvent: hexane, Rf = 0.42) gave intermediate compound (i) as a white solid (yield 92%).

The ¹ H-NMR and ¹⁹ F-NMR spectrum data of the intermediate compound (i) are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 2.31-2.48 (m, 2H, alkyl), 3.08 (t, J = 8.04 Hz, 2H, alkyl), 3.63 (s, 1H, alkyne)
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ: −144.44 to −144.62 (m, 2F, Ar), −136.93 to −137.11 (m, 2F, Ar), −126.59 To -126.75 (m, 2F, alkyl), -123.99 (s, 2F, alkyl), -123.40 (s, 2F, alkyl), -122.42 (s, 2F, alkyl),- 115.63 to −115.84 (m, 2F, alkyl), −81.28 (t, J = 11.00 Hz, 3F, alkyl)
These analytical data support the structure of the intermediate compound (i) represented by the chemical reaction formula (XIV).

Using the obtained intermediate compounds (i) and (g), 4,4′-bis [2,3,5,6-tetrafluoro-4- (2-perfluorohexylethyl) phenylethynyl) -perfluorodiphenyl The chemical reaction formula (XV) for obtaining acetylene (15) is shown below.

In a reactor substituted with nitrogen, terminal acetylene (i) (0.9 mmol, 0.47 g), diiodine (g) (0.30 mmol, 0.17 g), Pd (PPh ₃ ) ₄ (0 0.03 mmol, 35 mg) and CuI (0.03 mmol, 6 mg) were added and dissolved in toluene (8 ml) and diisopropylamine (0.8 ml) and stirred at 80 ° C. for 18 hours. After stirring, the reaction mixture was quenched with a saturated aqueous ammonium chloride solution and extracted three times with dichloromethane. The suspended organic layer was concentrated and dried under reduced pressure. Recrystallization and purification using toluene as a solvent gave the target product (15) as a white solid (yield 76%, melting point 239-242 ° C.).

The results of ¹ H-NMR, ¹⁹ F-NMR and HRMS analysis of the target product (15) are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 1.20 to 1.22 (m, 2H, alkyl), 2.66 (t, J = 7.50 Hz, 2H, alkyl)
¹⁹ F-NMR (282 MHz, C ₆ D ₅ CD ₃ , 110 ° C.) δ: −144.23 to −144.35 (m, 4F, Ar), −135.80 to −136.22 (m, 16F, Ar), -126.12 to -126.17 (m, 4F, alkyl), -123.26 to -123.30 (m, 4F, alkyl), -122.75 to -122.89 (m, 4F , Alkyl), −121.81 to −121.84 (m, 4F, alkyl), −114.70 (s, 4F, alkyl), −81.51 to −81.62 (m, 6F, alkyl)
HRMS (MALDI) Found (M +): 1357.9932 _{_{_{(calc: 1357.9961 (C 46 H 8 F}}} 42))
These analytical data support the structure of the acetylene compound (15) represented by the chemical reaction formula (XV).

(Example 5)
A chemical reaction formula (V) for obtaining trimethylsilylethynylpentafluorobenzene (b) as an intermediate compound for synthesizing the acetylene compound is shown below.

To a reactor purged with nitrogen, Pd (PPh ₃ ) ₄ (0.25 mmol, 0.29 g), CuI (0.25 mmol, 48 mg), pentafluorobromobenzene (5.0 mmol, 1.23 g) were added, and toluene was added. (20 ml) was dissolved in diisopropylamine (2 ml). Trimethylsilylacetylene (5.5 mmol, 0.77 ml) was added, and the mixture was stirred at 80 ° C. for 15 hours. Wash 3 times with saturated aqueous ammonium chloride and then extract 3 times with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over sodium sulfate, filtered through filter paper, concentrated and dried under reduced pressure. Thereafter, the product was purified by silica gel column chromatography (developing solvent: hexane, Rf = 0.50). A colorless liquid in which 8% of a triynesilylacetylene diyne was mixed was obtained (yield 80%).

The ¹ H-NMR and ¹⁹ F-NMR spectral data of the colorless liquid are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.30 (s, 9H, TMS)
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ: −162.29 to −162.48 (m, 2F, Ar), −152.86 (t, J = 20.6 Hz, 1F, Ar), −136. 24 to -136.36 (m, 2F, Ar)
These analytical data support the structure of the intermediate compound (b) represented by the chemical reaction formula (V).

The chemical reaction formula (XVI) for obtaining 1-trimethylsilylethynyl-2,3,5,6-tetrafluoro-4-butylbenzene (j) as an intermediate compound from the intermediate compound (b) is shown below. In the formula, Bu is an abbreviation for butyl group.

Trimethylsilylethynylpentafluorobenzene (b) (3.0 mmol) dissolved in THF was added to a reactor purged with nitrogen, cooled to 0 ° C., and n-butylmagnesium chloride (n-BuMgCl) (2.0 M tetrahydrofuran solution). , 4.5 ml, 9 mmol) was added dropwise. It returned to room temperature and stirred for 15 hours. After completion of stirring, the mixture was cooled to 0 ° C., quenched by adding an aqueous ammonium chloride solution, and washed three times with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over sodium sulfate, filtered through filter paper, concentrated and dried under reduced pressure. Thereafter, the product was purified by silica gel column chromatography (developing solvent: hexane, Rf = 0.50). A colorless liquid containing 3% of terminal acetylene and 8% of diyne of trimethylsilylacetylene was obtained (yield 83%).

The ¹ H-NMR and ¹⁹ F-NMR spectral data of the colorless liquid are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.27 (s, 9H, TMS), 0.93 (t, J = 7.14 Hz, 3H, alkyl), 1.29 to 1.42 (m, 2H, alkyl), 1.51-1.62 (m, 2H, alkyl), 2.72 (t, J = 7.50 Hz, 2H, alkyl)
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ: −145.50 to −145.72 (m, 2F, Ar), −138.25 to −138.48 (m, 2F, Ar)
These analytical data support the structure of the intermediate compound (J) represented by the chemical reaction formula (XVI).

The chemical reaction formula (VI) for obtaining perfluorodiphenylacetylene (c) as an intermediate compound from the intermediate compound (b) is shown below.

Pd (PPh ₃ ) ₄ (0.10 mmol, 0.12 g), CuCl (2.4 mmol, 0.24 g), pentafluoroiodobenzene (2.0 mmol, 0.49 g) were added to the reactor substituted with nitrogen. Dissolve in dry DMF (4 ml), diisopropylamine (0.40 ml). Trimethylsilylethynylpentafluorobenzene (b) (2.4 mmol, 0.63 mg) obtained in the above synthesis was added and stirred at 80 ° C. for 15 hours. The extract was washed 3 times with a saturated aqueous ammonium chloride solution and then extracted 3 times with ethyl acetate. The extract was dried over sodium sulfate, filtered through filter paper, concentrated and dried under reduced pressure. The product was purified by silica gel column chromatography (developing solvent: hexane, Rf = 0.43). Subsequently, recrystallization purification with hexane was performed to obtain the intermediate compound (c) as a white solid (yield 49%).

Using the obtained intermediate compounds (j) and (c), 4,4′-bis (2,3,5,6-tetrafluoro-4-n-butylphenylethynyl) -perfluorodiphenylacetylene (16) is obtained. The chemical reaction formula (XVII) to be obtained is shown below.

A reactor substituted with nitrogen was charged with 1-trimethylsilylethynyl-2,3,5,6-tetrafluoro-4-butylbenzene (j) (1.5 mmol), perfluorodiphenylacetylene (c) (0.5 mmol, 0 .18 g) was added and dissolved in THF (5 ml). After cooling to 0 ° C., TBAF (1.0 M tetrahydrofuran solution, 0.10 ml, 0.10 mmol) was added dropwise and stirred for 18 hours. After stirring, the reaction mixture was quenched with water and extracted three times with dichloromethane. The suspended organic layer was concentrated and dried under reduced pressure. The obtained residue was subjected to gel filtration using a toluene solvent, and then recrystallized and purified using THF as a solvent to obtain the target product (16) as a yellow solid (yield 44%, melting point 215). -217 ° C).

The results of ¹ H-NMR, ¹⁹ F-NMR, and HRMS analysis of the target product (16) are shown below.
¹ H-NMR (300 MHz, C ₆ D ₆ , 75 ° C.) δ: 0.78 (t, J = 7.14 Hz, 3H, alkyl), 1.10 to 1.17 (m, 2H, alkyl), 1 .32 to 1.37 (m, 2H, alkyl), 2.40 (t, J = 7.68 Hz, 2H, alkyl)
¹⁹ F-NMR (282 MHz, C ₆ D ₆ , 75 ° C.) δ: −144.60 to −144.79 (m, 4F, Ar), −137.008 to −137.26 (m, 4F, Ar) , −135.92 to −136.09 (m, 8F, Ar)
HRMS (EI) Found (M +): 778.1158 (calculated value: 778.1153 (C ₃₈ H ₁₈ F ₁₆ ))
These analytical data support the structure of the acetylene compound (16) represented by the chemical reaction formula (XVII).

(Cyclic voltammetry (CV) measurement)
Add 10 mL of 0.1 M tetrabutylammonium hexafluorophosphate / tetrahydrofuran solution to an electrolytic cell with glassy carbon as the working electrode, platinum wire as the auxiliary electrode, and silver / silver perchlorate (0.1 M acetonitrile solution) as the reference electrode. The acetylene compounds of Examples 1 to 5 were added to a concentration of 1 mM. A potentiostat / galvanostat HAB-151 manufactured by Hokuto Denko Co., Ltd. was connected to each electrode of this electrolytic cell, and cyclic voltammetry (CV) measurement was performed by sweeping at a speed of 0.1 V / second. First reduction potentials of acetylene compounds (1), (7), (14), (15), and (16) obtained in Examples 1 to 5 with potentials corrected with a ferrocene electrode, and typical N-type organic compounds the first reduction potential of phenyl _{C 60} butyric acid methyl which is one of semiconductor (PCBM) (Organic Letters, 2007,9 Vol, No. 4, pp. 551-554) are shown in Table 1.

From the results shown in Table 1, the acetylene compounds (1), (7), (14), (15) and (16) of the present invention obtained in Examples 1 to 5 have the properties of N-type organic semiconductors. I understood.

The acetylene compound of the present invention is useful as a semiconductor material for organic electronic devices such as field effect transistors, organic electroluminescence, printable circuits, organic capacitors, and organic solar cells, and is used as an organic semiconductor exhibiting N-type characteristics.

Claims

The following chemical formula (I)

(In the formula, at least four of R 1 to R 16 , X 1 and X 2 are the same or different from each other, and are linear, branched and / or cyclic perfluoroalkyl groups having 1 to 20 carbon atoms. Or a fluorine atom, and the remainder is a linear, branched and / or cyclic hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom which may be the same or different from each other and may have a substituent. An acetylene compound represented by the formula:
2. The X 1 and X 2 are the same or different perfluoroalkyl groups, and the R 1 to R 16 are at least four of which are fluorine atoms. Acetylene compounds.
An N-type organic semiconductor material comprising the acetylene compound according to claim 1.