JP4582286B2 - Sulfooxyalkynylthiophene compound and process for producing the same - Google Patents

Description

  The present invention relates to a monomer of a π-conjugated conductive polymer material.

  Conventionally, many π-conjugated conductive polymers having a sulfonic acid group are known. For example, self-doped polythiophene is generally applied to electron beam lithography (see Non-Patent Document 1 and Non-Patent Document 2). .) In addition, poly (3-thiophene-β-butanesulfonate) and poly (3-thiophene-β-ethanesulfonate) are known as water-soluble self-doped polythiophenes used for antistatic applications (non-patent literature). 1 and Non-Patent Document 3).

  However, the sulfooxyalkynylthiophene compounds of the present invention have not been reported yet. There is no example of oxidative polymerization.

  In addition, as a hydroxy alkynyl thiophene compound, when n and m are 1, Formula [9]

3- [4- (3-Hydroxy-prop-1-ynyl) -thiophen-3-yl] -prop-2-yn-1-ol (3,4HTPO) represented by 1).
International Publication No. 01/19809 pamphlet (pages 21, 27 and 41-42) “Synth. Met.” (Netherlands), Elsevier Sequoia, 1989, Volume 30, p. 305-319 “Handbook of Conducting Polymers”, second edition, revised and augmented (USA), Marcel Deckers, Inc., 1998, p. 930 "J. Amer. Chem. Soc.", (USA), American Chemical Society, 1987, Vol. 109, p. 1858-1859

  An object of the present invention is to provide a π-conjugated conductive polymer monomer capable of oxidative polymerization.

  The present inventors have intensively studied to solve the above problems.

  That is, the first aspect of the present invention is the formula [1]

(In the formula, R represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom, and n and m represent an integer of 1 to 3.)
It is a sulfooxyalkynyl thiophene compound represented by these.

  Here, in the formula [1], n represents 1 and m represents an integer of 1 to 3. More specifically, in the formula [1], n is 1 and m is 1.

  A second aspect of the present invention provides the formula [2]

(In the formula, X represents a halogen atom, R represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom, and n and m represent an integer of 1 to 3).
It is a sulfooxyalkynyl halogenothiophene compound represented by these.

  Here, in the formula [2], the compound in which n represents 1 and m represents an integer of 1 to 3 is exemplified. More specifically, in the formula [2], n is 1 and m is 1.

  A third aspect of the present invention provides the formula [3]

(In formula, n and m represent the integer of 1-3.)
Using a sulfur trioxide compound for the hydroxyalkynylthiophene compound represented by formula [4]

(In the formula, n and m have the same meaning as described above.)
A sulfooxyalkynylthiophene compound represented by the formula [5], which is reacted with an alkali metal compound or an alkaline earth metal compound

(In the formula, M represents an alkali metal atom or an alkaline earth metal atom, and n and m represent the same meaning as described above.)
Is a method for producing a sulfooxyalkynylthiophene metal salt compound represented by the formula:

  Here, in the formula [5], a method for producing the compound in which n represents 1 and m represents an integer of 1 to 3 can be mentioned. More specifically, in the formula [5], the production method of the compound in which n is 1 and m is 1 can be mentioned.

  And the 4th viewpoint of the present invention is a formula [6].

(In the formula, X represents a halogen atom, and n and m represent an integer of 1 to 3.)
A sulfur trioxide compound is reacted with a hydroxyalkynyl halogenothiophene compound represented by the formula [7]

(In the formula, X, n and m have the same meaning as described above.)
A sulfooxyalkynylhalogenothiophene compound represented by formula (8) is reacted with an alkali metal compound or an alkaline earth metal compound [8]

(In the formula, M represents an alkali metal atom or an alkaline earth metal atom, and X, n and m represent the same meaning as described above.)
Is a method for producing a sulfooxyalkynyl halogenothiophene metal salt compound represented by the formula:

  Here, in the formula [8], n is 1 and m is a production method of the compound representing an integer of 1 to 3. More specifically, in the formula [8], the production method of the compound in which n is 1 and m is 1 can be mentioned.

  According to the present invention, a useful π-conjugated conductive polymer monomer capable of oxidative polymerization can be provided.

  Hereinafter, the present invention will be described in detail.

  In the above formulas [1] to [8], the case where n and m are 1 will be described.

  The production method of the compound of the present invention is represented by the following four reaction schemes as described above.

(In the formula, X represents the same meaning as described above, and MY represents an alkali metal compound or an alkaline earth metal compound.)
Hereinafter, the schemes (1) and (3) will be described in order.

  First, a method for producing 3,4HTPO as a raw material is represented by the following reaction scheme described in WO 01/19809.

(In the formula, X represents the same meaning as described above.)
Examples of raw material 3,4-dihalogeno-thiophene (3,4DXT) include 3,4-difluoro-thiophene, 3,4-dichloro-thiophene, 3,4-dibromo-thiophene, and 3,4-iodo-thiophene. 3,4-dibromo-thiophene is preferable from the viewpoint of reactivity and economy.

  The other raw material is propargyl alcohol, and these can be used as they are.

As the catalyst, Pd (Ph ₃ P) ₄ (2 + 1 mol%) and CuI (3 + 1.5 mol%) and n-propylamine as a solvent were heated to reflux, and then purified by silica gel column chromatography to obtain 3,4HTPO. Is obtained.

  In the pamphlet of WO 01/19809, the intermediate 3, 4BTPO was not described. However, the present inventors purified the reaction product by silica gel column chromatography to obtain 3 and 4 HTPO. -(4-Halogeno-thiophen-3-yl) -prop-2-yn-1-ol (3,4XTPO) was isolated and confirmed by structural analysis.

Now, sulfur trioxide (SO ₃ ) is used as a sulfonating agent for 3,4HTPO and 3,4XTPO alcohols to sulfonic acid esters. As the form thereof, in addition to sulfur trioxide alone (itself), complexes with N, N-dimethylformamide (DMF), 1,4-dioxane, pyridine and the like can also be used. The amount used is preferably 1 to 1.5 molar equivalents relative to the hydroxy group of the raw material.

  Examples of the solvent include amides such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone (DMI). Compounds, ether compounds such as tetrahydrofuran (THF), 1,2-dimethoxyethane and 1,4-dioxane. In particular, DMF and DMAc are preferable. The amount used is preferably 1 to 10 times, more preferably 2 to 5 times the weight of the substrate.

  The reaction temperature can be 0 to 150 ° C., but 10 to 100 ° C. is particularly preferable.

  The reaction time can be determined from the analysis result of the reaction solution such as liquid chromatography, and is usually completed in 1 to 5 hours.

  After completion of the reaction, the solvent is distilled off by concentration, and the residue is extracted by adding acetone to remove excess sulfur trioxide complex crystals, and then concentrated, and then the crude product is dissolved in ethyl acetate and water. Liquid, unreacted raw material is separated into an ethyl acetate layer, and the aqueous layer is concentrated to give the desired 3- [4- (3-sulfooxy-prop-1-ynyl) -thiophen-3-yl] -prop-2-ynyl hydrogen Sulfate (3,4 STHS) and 3- (4-halogeno-thiophen-3-yl) -prop-2-ynyl hydrogen Sulfate (3,4 XTPS) sulfooxyalkynyl thiophene compounds are obtained.

  Next, a method for producing sulfooxyalkynylthiophene metal salt compounds by the reaction of metal compounds with the sulfooxyalkynylthiophene compounds of Schemes (2) and (4) will be described.

  The metal compound represents an alkali metal compound or an alkaline earth metal compound in the periodic table, for example, hydroxides such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium and barium, carbonates and organic Examples include acid salts. Specifically, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, calcium bicarbonate, formic acid Examples thereof include sodium, potassium formate, magnesium formate, calcium formate, sodium acetate, potassium acetate, magnesium acetate, and calcium acetate.

  Among these, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, sodium bicarbonate, potassium bicarbonate and the like are particularly preferable.

  The amount of these used is preferably 1 to 2 molar equivalents, particularly preferably 1 to 1.5 molar equivalents, relative to the sulfone group of the substrate.

  Examples of the solvent include water that dissolves the substrate and the metal compound, for example, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methylpyrrolidone, and 1,3-dimethyl-2- An imide compound such as imidazolidinone (DMI) can be used alone or as a mixed solvent with water. The amount used is preferably 1 to 10 times, more preferably 2 to 5 times the weight of the substrate.

  The reaction temperature can be -20 to 50 ° C, but 0 to 40 ° C is particularly preferable.

  The reaction time can be determined from the analysis result of the reaction solution such as liquid chromatography, and can usually be completed in 0.5 to 5 hours.

  After completion of the reaction, the solvent is distilled off by concentration, methanol is added to the residue for extraction, the excess metal compound is removed, the solution is concentrated, and ethanol is added to the residue for crystallization to obtain the target M3,4TPS and M3,4XTS sulfothiophene metal salt compounds are obtained.

  In addition, the sulfonation reaction liquid of the schemes (1) and (3) can be directly subjected to the metal chloride reaction of the schemes (2) and (4).

  The reaction and purification of the present invention described above can be performed batchwise or continuously.

  The reaction can be carried out at normal pressure or at elevated pressure.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

  The analytical methods used in the examples are as follows.

[1] [Gas chromatography (GC)]
Model: Shimadzu GC-17A, Column: Capillary column CBP1-W25-100 (25 mx 0.53 mm φx 1μm), Column temperature: 100 ℃ (holding 2 min.)-8 ℃ / min. (Raising rate) -290 ℃ (Holding 10 min.), Inlet temperature: 290 ° C, detector temperature: 290 ° C, carrier gas: helium, detection method: FID method.
[2] [Mass Spectrometry (MASS)]
Model: LX-1000 (JEOL Ltd.), Detection method: FAB method.
[3] [ ¹ H NMR]
Model: INOVA500 (VARIAN Corp.), Measuring solvent: CDCl ₃
Standard substance: tetramethylsilane (TMS).
[4] [ ¹³ C NMR]
Model: INOVA500 (VARIAN Corp.), Measuring solvent: CDCl ₃
Reference material: CDCl ₃ (δ: 77.1 ppm).
[5] [Melting point (mp)]
Measuring instrument: MP-J3 (Yanako Instrument Development Laboratory).

    Example 1

  Into a 300 mL four-necked reaction flask, 25.0 g (103 mmol) of 3,4-dibromo-thiophene (3,4 DBT) and 100 g of n-propylamine were charged, and while stirring at 25 ° C., 2.38 g of tetrakistriphenylphosphine palladium (2 0.06 mmol) and 0.588 g (3.09 mmol) of copper iodide were added, and then 17.3 g (309 mmol) of propargyl alcohol was added dropwise over 10 minutes. The mixture was stirred as it was at 25 ° C. for 1 hour, and further stirred in an oil bath at 70 ° C. (internal temperature 54 ° C.) for 7 hours. Subsequently, 1.19 g (1.03 mmol) of tetrakistriphenylphosphine palladium and 0.29 g (1.10 mmol) of copper iodide were added, and 8.7 g (155 mmol) of propargyl alcohol was added dropwise. Again, the mixture was stirred for 20 hours in a 70 ° C. oil bath (internal temperature 57 ° C.). After completion of the reaction, the reaction mixture was concentrated, the residue was dissolved in ethyl acetate and water, the insoluble matter was removed by Celite filtration, and the organic layer obtained by liquid separation was concentrated to obtain 37.5 g of an oily substance. As a result of analyzing this oily substance by gas chromatography, a new peak A appeared as 40.8 area%, and a new peak B appeared as 23.3 area%. This was purified by column chromatography using 140 g of silica gel (eluent / ethyl acetate: n-heptane = 1: 9 to 1: 5) to obtain 16.0 g (purity 70.6%) Yield 57%) and 4.56 g (purity: 76.5%) (yield: 23.7%) of fraction 2.

  Furthermore, 16.0 g (purity 70.6%) of the oily product of fraction 1 was re-purified by column chromatography (eluent / ethyl acetate: n-heptane = 1: 9 to 1: 5) using 140 g of silica gel. 10.3 g (purity 93.0%) of an oily product of fraction 6 (recovery rate 84.7%) was obtained. This oily substance was confirmed to be 3- (4-bromo-thiophen-3-yl) -prop-2-yn-1-ol (3,4BTPO) from the following analysis results.

[3,4BTPO]
¹ H NMR (CDCl ₃ , δppm): 4.43 (s, 2H), 7.13 (d, J = 3.36Hz, 1H), 7.36 (d, J = 3.67Hz, 1H).
¹³ C NMR (CDCl ₃ , δ ppm): 51.2564, 78.5646, 90.6355, 113.3275, 123.8113, 122.9033, 127.1915.
On the other hand, 4.56 g (purity 76.5%) of the oily product of fraction 2 was purified again by column chromatography (eluent / ethyl acetate: n-heptane = 1: 9 to 1: 5) using 40 g of silica gel. 1.0 g (purity 90.6%) of an oily product of fraction 7 was obtained.

  This oily product is 3- [4- (3-hydroxy-prop-1-ynyl) -thiophen-3-yl] -prop-2-yn-1-ol (3,4HTPO) from the following analysis results. It was confirmed.

[3,4HTPO]
MASS (FAB ⁺ , m / e (%)): 191 ([MH] ⁺ , 3), 174 (29), 146 (62), 102 (100).
¹ H NMR (CDCl ₃ , δ ppm): 4.45 (s, 4H), 7.31 (s, 2H).
¹³ C NMR (CDCl ₃ , δ ppm): 50.9736 (2C), 78.9914 (2C), 89.8720 (2C), 124.0855 (2C), 128.3813 (2C).

Example 2

  In a 100 mL glass four-necked reaction flask, 12.0 g (55.3 mmol) 3- (4-bromo-thiophen-3-yl) -prop-2-yn-1-ol (3,4BTPO) and N, N- 40 g of dimethylformamide (DMF) was charged, and 11.0 g (71.9 mmol) of sulfur trioxide / DMF complex was added in portions over 30 minutes while stirring at 10 ° C. After gradually returning to room temperature and stirring at 40 ° C. for 2 hours, LC analysis revealed that raw material 3,4BTPO disappeared and 3- (4-bromo-thiophen-3-yl) -prop-2-ynyl hydrogen sulfate (3 , 4BTPS). Subsequently, the reaction solution was cooled to 10 ° C. with stirring, and 12.1 g (144 mmol) of sodium bicarbonate was added in 20 minutes while paying attention to foaming. Subsequently, DMF was distilled off by concentration, and methanol was added to the obtained oily substance, followed by heating and stirring. As a result, solid content was suspended. The solid was removed by Celite filtration, and the filtrate was concentrated to obtain 20.8 g of a solid. Again, 40 g of methanol was added to the solid and the mixture was slightly concentrated with warming and stirring. After addition of ethanol, crystals were precipitated, and the mixture was warmed and stirred as it was and then cooled with ice. Filtration, ethanol washing and drying gave 12.5 g of crystals (yield 71.2%).

  This product was confirmed to be sodium 3- (4-bromo-thiophen-3-yl) -prop-2-ynyl sulfate (S3,4BTS) from the following results.

[S3, 4BTS]
MASS (FAB ⁺ , m / e (%)): 343 ([M + H] ⁺ , 37), 176 (100).
¹ H NMR (DMSO-d ₆ , δppm): 4.59 (s, 2H), 7.76 (d, J = 3.36Hz, 1H), 7.95 (d, J = 3.36Hz, 1H).
¹³ C NMR (DMSO-d ₆ , δppm): 54.2183, 78.6195, 88.1419, 112.1615, 122.5919, 124.6902, 131.7786.
mp. (° C): 161-163
Na, S, Br content analysis (wt%): Na 7.19, S 19.11, Br 27.05 ( theoretical value: as _{C 7 H 4 BrO 4 S 2} Na, Na7.20, S 20.10, Br 25.04) ( measuring instrument: ESEM -EDAX).

Example 3

  3.14 g 3- [4- (3-hydroxy-prop-1-ynyl) -thiophen-3-yl] -prop-2-yn-1-ol (3,4HTPO) in a 50 ml glass four-necked reaction flask (16.3 mmol) and 12.6 g of N, N-dimethylformamide (DMF) were charged, and 6.2 g (39 mmol) of sulfur trioxide / pyridine complex was added in portions over 10 minutes at 5 ° C. with stirring. Subsequently, stirring was continued at 20 ° C. for 1 hour, and LC analysis revealed that raw materials 3, 4HTPO disappeared and a product appeared.

  Subsequently, 6.57 g (78.2 mmol) of sodium bicarbonate was added with stirring at 20 ° C., and stirring was continued for 1 hour. The residue was further obtained by concentration under reduced pressure in a 50 ° C. water bath. When 50 g of methanol was added to the residue and the mixture was heated to 50 ° C., a solid substance was precipitated, which was ice-cooled and filtered through Celite. The filtrate was concentrated and dried to obtain 10.3 g of a paste. After adding methanol to this crude material and re-dissolving it, it was concentrated to form a gel. After adding 50 g of ethanol and heating to 50 ° C., cooling on ice, filtering and washing with ethanol, and further drying, LC Analysis gave 6.23 g (67.4% yield) of single-peak gray crystals. This crystal is sodium 3- [4- (3-sodiumsulfooxy-prop-1-ynyl) -thiophen-3-yl] -prop-2-ynyl sulfate (S3,4TPS) from the following results. confirmed.

[S3, 4TPS]
¹ H NMR (DMSO-d ₆ , δppm): 4.79 (s, 4H), 7.55 (s, 2H).
¹³ C NMR (DMSO-d ₆ , δppm): 59.7048, 83.5489, 88.1270, 125.0874, 133.9307.
mp. (° C): 146-147
Na, S content analysis (wt%): Na 11.06, S 21.98 (theoretical value: C _10. H ₆ O ₈ S ₃ Na ₂ , Na 11.61, S 24.24) (measuring instrument: ESEM-EDAX).

Claims (10)

Formula [1]

(In the formula, R represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom, and n and m represent an integer of 1 to 3).
A sulfooxyalkynylthiophene compound represented by: Formula [2]

(In the formula, R represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom, X represents a halogen atom, and n and m represent an integer of 1 to 3.)
A sulfooxyalkynyl halogenothiophene compound represented by: Formula [3]

(In formula, n and m represent the integer of 1-3.)
A sulfur trioxide compound is reacted with a hydroxyalkynylthiophene compound represented by the formula [4]

(In formula, n and m represent the integer of 1-3.)
A sulfooxyalkynylthiophene compound represented by the formula [5], which is reacted with an alkali metal compound or an alkaline earth metal compound

(In the formula, M represents an alkali metal atom or an alkaline earth metal atom, and n and m represent an integer of 1 to 3).
The manufacturing method of the sulfooxy alkynyl thiophene metal salt compound represented by these. Formula [6]

(In the formula, X represents a halogen atom, and n and m represent an integer of 1 to 3.)
A sulfur trioxide compound is reacted with a hydroxyalkynyl halogenothiophene compound represented by the formula [7]

(In the formula, X represents a halogen atom, and n and m represent an integer of 1 to 3.)
A sulfooxyalkynyl halogenothiophene compound represented by the formula [8] is obtained, and then reacted with an alkali metal compound or an alkaline earth metal compound.

(In the formula, M represents an alkali metal atom or an alkaline earth metal atom, X represents a halogen atom, and n and m represent an integer of 1 to 3).
The manufacturing method of the sulfooxyalkynyl halogenothiophene metal salt compound represented by these. The sulfooxyalkynylthiophene compound according to claim 1 , wherein an alkali metal atom is sodium or potassium as R in the formula [1] . The sulfooxyalkynyl halogenothiophene compound according to claim 2 , wherein the alkali metal atom is R or R in the formula [2] . The process for producing a sulfooxyalkynylthiophene metal salt compound according to claim 3 , wherein M in the formula [5] is an alkali metal atom of sodium or potassium. The method for producing a sulfooxyalkynylhalogenothiophene metal salt compound according to claim 4 , wherein M in the formula [8] is an alkali metal atom or sodium or potassium. 4. The method for producing a sulfooxyalkynylthiophene metal salt compound according to claim 3, wherein the sulfur trioxide compound is a sulfur trioxide / pyridine complex . The method for producing a sulfooxyalkynyl halogenothiophene metal salt compound according to claim 4 , wherein the sulfur trioxide compound is a DMF (N, N-dimethylformamide) complex .