JPH06166746A - Thiophene-silole copolymer and its production - Google Patents

Abstract

(57) [Summary] [Objective] To provide a novel thiophene-silole copolymer having a potential for a photofunctional material and a method for producing the same. [Structure] A thiophene-silole copolymer represented by the following Chemical Formula 1 and a method for producing the same; However, R in the chemical formula 1 is a monovalent hydrocarbon group having 1 to 7 carbon atoms or a hydrogen atom; A and B are an alkyl group, an aromatic group,
An alkenyl group or an aliphatic group in which A and B are combined to form a ring, m and p are integers of 1 or more, n is an integer of 0 or more, X is a hydrogen atom or a halogen atom, and Y is a hydrogen atom, It is a halogen atom or thiophene.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thiophene copolymer which is a π-electron conjugated organic compound and a method for producing the same.
In particular, it relates to a novel thiophene-silole copolymer having a light absorption band in the visible region and a method for producing the same.

[0002]

2. Description of the Related Art As examples of π-electron conjugated organic compounds, there have been reported some compounds having considerably high stability such as polyacetylene, polythiophene and polypyrrole. Further, in recent years, in addition to homopolymers, various copolymers such as combinations of thiophene and pyridine have been synthesized, and they show a unique ultraviolet absorption spectrum due to the contribution of intramolecular donor-acceptor structure of electrons. , Is attracting attention as a potential new functional material. On the other hand, since the silole skeleton has a structure that can function as both an electron donor and an electron acceptor, it has been developed into a polymer, but it has not been sufficiently studied.

[0003]

Therefore, the present inventors have tried to introduce a silole skeleton into polythiophene, and as a result, obtain a stable thiophene-silole copolymer having an absorption band in the visible light region. As a result, they have reached the present invention. Therefore, the first object of the present invention is to provide a novel thiophene-silole copolymer having potential as a photofunctional material. A second object of the present invention is to provide a method for producing a novel thiophene-silole copolymer.

[0004]

The above objects of the present invention have been achieved by a thiophene-silole copolymer represented by the following chemical formula 5 and a method for producing the same.

[Chemical 5] However, R in Chemical formula 5 is a monovalent hydrocarbon group or hydrogen atom having 1 to 7 carbon atoms, A and B are alkyl groups, aromatic groups, alkenyl groups, or A and B are bonded to form a ring. Is an aliphatic group, m and p are integers of 1 or more, n is an integer of 0 or more, X is a hydrogen atom or a halogen atom, and Y is a hydrogen atom, a halogen atom or thiophene.

The thiophene-silole copolymer of the present invention is obtained by reacting a compound represented by the following chemical formula 6 with a compound represented by the following chemical formula 7 in the presence of a nickel or palladium metal complex. It can be easily obtained.

[Chemical 6] In the formula, R, A and B are the same as those in Chemical formula 5, X'is a halogen atom and Y'is a halogen atom or a hydrogen atom. Also, a and b are integers of 0 or more.

[0006]

[Chemical 7] In the formula, R, A and B are the same as those in Chemical formula 5, and M is S
nR ₃ , B (OH) ₂ , BX ₂ , MgX or ZnX,
M ′ is SnR ₃ , B (OH) ₂ , BX ₂ , MgX, Zn
X or a hydrogen atom. Further, c and d are integers of 0 or more, m is a + c, n is b + d, and X is a hydrogen atom or a halogen atom.

Here, R in the general formula is a methyl group,
In addition to alkyl groups such as ethyl group, propyl group and hexyl group, phenyl group, tolyl group, naphthyl group, vinyl group,
A 3,3,3-trifluoropropyl group and the like can be mentioned. Further, from the viewpoint of ease of synthesis, A and / or B
Preferably has a functional group such as alcohol, ester, amide, or amine, and particularly preferably has an aliphatic group from the viewpoint of improving the solubility of the copolymer of the present invention.

Particularly excellent properties are exhibited when A and B are bonded to each other to form a 5-membered ring. As a specific example in such a case, for example, the following chemical formula 8 can be mentioned.

[Chemical 8] However, R in the chemical formula 8 is the same as R in the chemical formula 5, R ′ is a monovalent organic group having 1 to 12 carbon atoms or a silicon group substituted with an organic group, and n ′ is 0 or more. Is an integer.

As the halogen atom in the general formula,
Examples thereof include chlorine, bromine, and iodine atoms, but a bromine atom is most preferable from the viewpoint of easy handling and reactivity.
The above M is a tri-substituted tin group, and examples thereof include a trimethylstannyl group, a tributylstannyl group, and a triphenylstannyl group. For example, the compound of the chemical formula 8 is a bromide represented by the chemical formula 9 below, which is obtained by treating the corresponding 2,5-dithienylsilole with N-succinimide bromide, or the like.
It is easily obtained by reacting dithienylsilole with n-butyllithium and then reacting with a tin compound represented by the following Chemical formula 10 obtained by a known method such as adding trialkyltin chloride. be able to.

[0010]

[Chemical 9]

[Chemical 10]

The metal complex of palladium or nickel is
It is an essential catalyst for obtaining the compound of Chemical formula 5 of the present invention, and examples thereof include the general formula X ₂ M (PR ¹ ₃ ) ₂
Alternatively, those represented by X ₂ M (R ² ₂ PQPR ³ ₂ ) and the like can be mentioned. However, where M is Pd or N
i and X are Cl, Br or I, R ¹ , R ² and R ³ are alkyl or aryl groups such as phenyl and substituted phenyl.

As a concrete example of the former, Cl ₂ Pd (PM
e ₃ ) ₂ , Cl ₂ Pd (PEt ₃ ) ₂ , Cl ₂ Pd (P
Bu ₃ ) ₂ , Cl ₂ Pd (PPh ₃ ) ₂ , Cl ₂ Pd
(P (OMe) ₃ ) ₂ , Cl ₂ Pd (P (OEt) ₃ )
₂ ; Cl ₂ Ni (PMe ₃ ) ₂ , Cl ₂ Ni (PE
t ₃ ) ₂ , Cl ₂ Ni (PBu ₃ ) ₂ , Cl ₂ Ni (P
Ph ₃ ) ₂ , Cl ₂ Ni (P (OMe) ₃ ) ₂ , Cl ₂
Ni (P (OEt) ₃ ) ₂ etc. are available;

Specific examples of the latter having a divalent ligand include Cl ₂ Pd (Ph ₂ P (CH ₂ ) ₄ PPh ₂ ), C
l ₂ Pd (Ph ₂ P (CH ₂ ) ₃ PPh ₂ ), Cl ₂ P
d (1,1′-bis (diphenylphosphino) ferrocene), Cl ₂ Ni (Ph ₂ P (CH ₂ ) ₃ PPh ₂ ),
Cl ₂ Ni (Ph ₂ P (CH ₂ ) ₄ PPh ₂ ) and the like can be mentioned.

As another example, Pd (PP
h₃)_Four, (PhCH₂) PdCl (PR¹ ₃)₂, C
l₂Pd (MeCN)₂, Cl₂Pd (PhCN)₂,
Cl₂Pd (MeCN) PR₃, Cl₂Pd (PhC
N) PR₃, [Pd (π-C₃H₃) Cl]₃And Ni
(Acac)₂Is mentioned. PdCl₂, Pd (OA
c)₂Or Pd₂(DBA)_FourAnd R¹ ₃P or R² ₂PQ
PR³ ₂It is also effective to use in combination with.
Furthermore, Ph₃As can also be used. However, the above formula
In, Me is a methyl group, Et is an ethyl group, and Bu is a butyl group.
And Ph are phenyl groups, and acac is acetylacetone.
And DBA represent dibenzalacetone.

When the oligomer obtained by the present invention was compared with a polythiophene oligomer, it was confirmed that the introduction of one silole ring causes a long wavelength shift in the ultraviolet absorption spectrum, which is comparable to three thiophene rings. This is because the copolymer of the present invention is a combination of an electron-donating thiophene and an electron-accepting silole. As described above, the novel compound of the present invention has an absorption band in the visible light region due to a specific interaction of the π-electron system, and is expected to be applied to an optical functional material.

[0016]

Since the novel copolymer of the present invention has a specific light absorption band in the visible region, it is promising as a future photofunctional material such as a photoresponsive material and an energy storage material.

[0017]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. However, Me in Chemical formulas 11 to 17 represents a methyl group, Ph represents a phenyl group, and Bu in Chemical formula 16 represents C ₄ H ₉ .

Synthesis Example 1. A 200 ml flask equipped with a cooling base, a dropping funnel, and a stirrer has the structural formula shown below.
2,5-dithienylsilole represented by 1 (hereinafter TST
1.45 g of tetrahydrofuran and 40 ml of tetrahydrofuran were added, and 20 ml of a dimethylformamide solution of 0.85 g of N-bromosuccinimide was added dropwise.

[Chemical 11]

After completion of dropping the dimethylformamide solution 1
After 0 minutes, 100 ml of water was added to terminate the reaction, and the mixture was extracted three times with 100 ml of hexane. The organic layers were collected, washed with water and brine, and dried over sodium sulfate. After distilling off the solvent, silica gel column chromatography (eluent: hexane / methylene chloride = 10/1, Rf = 0.
38) was used to obtain 1.2 g of dibromide represented by the following Chemical formula 12.

[0020]

[Chemical 12] The obtained bromide was a yellow crystal having a melting point of 145 to 147 ° C. The result of elemental analysis shows that carbon atoms are 55.3.
6%, 6.02% hydrogen atoms, and C ₄₁ H ₅₂ O ₂ S ₂
In good agreement with the calculated values of 55.64% and 5.92% when Si ₃ Br ₂ was used.

¹ H NMR (200 MHz, CDCl
₃ solvent) measurement result δ is 0.03 (s, 12H),
0.89 (s, 18H), 2.59 (s, 4H), 3.
56 (s, 4H), 6.52 (d, J = 3.9Hz, 2
H), 6.81 (d, J = 3.9 Hz, 2H), 7.1
0-7.50 (m, 6H), 7.60-7.70 (m,
4H) and ¹³ C NMR (50 MHz, CDCl ₃ ).
The measurement results δ of 5.46, 18.34, 25.94,
36.02, 52.66, 65.45, 111.46,
124.23, 126.21, 128.40, 130.
14, 130.47, 131.61, 135.79, 1
It was 44.63 and 158.64.

Incidentally, TST was synthesized as shown in Chemical Formula 13 below.

[Chemical 13]

Synthesis Example 2. Dithienylsilole 8 having a structural formula of the following Chemical Formula 14, produced in exactly the same manner as in Synthesis Example 1 except that the reaction amount of N-bromosuccinimide was 1 equivalent.
In a 1 mg dry ether solution under nitrogen atmosphere at -70 ° C.
And a 1.67 mol hexane solution of n-butyllithium 12
0 μl was added. After stirring at −70 ° C. for 1 hour, 60 μl of chlorotributyltin was added, and the mixture was further stirred for 1 hour until it returned to room temperature.

[Chemical 14]

In addition to the dispersion liquid thus obtained,
4 ml of a dry tetrahydrofuran solution containing 86 mg of dithienylsilole of the above chemical formula 14 and Cl ₂ Pd (PPh ₃ ) ₂ 4
μg was added. After warming to 65 ° C. and stirring for 5 days, the mixture was filtered through Celite. The filtrate is concentrated and passed through a silica gel column (eluent: hexane / methylene chloride = 3 /
By 1), the compound represented by the following chemical formula 15
9 mg was obtained.

[Chemical 15]

From the ultraviolet-visible absorption spectrum data,
The compound obtained was found to have a maximum absorption wavelength at 505 nm. The elemental analysis shows that carbon atoms are 6
7.71%, hydrogen atoms 7.29%, C ₈₂ H ₁₀₆
Calculated values for O ₄ S ₄ Si ₆ 67.81%
And 7.36%.

Furthermore, ¹ HNMR (200 MH _Z , CDC
The measured value δ of l ₃ ) is 0.03 (s, 24H), 0.9
0 (s, 36H), 2.68 (br.s, 8H), 3.
60 (s, 8H), 6.68 (d, J = 3.9H Z, 2
H), 6.82 (dd, J = 1.0 and 3.7H _Z, 2
H), 6.89 (d, J = 3.9H Z, 2H), 6.8
9 (dd, J = 3.7 and 5.1H _Z, 2H), 7.1
8 (dd, J = 1.0 and 5.1H _Z, 2H), 7.3
0-7.48 (m, 12H), 7.64-7.74
(M, 8H);

The measured value δ of ¹³ CNMR (50 MH _Z , CDCl ₃ ) is −5.42, 18.37, 25.97, 3
6.34, 52.66, 65.47, 123.17, 1
24.07, 124.55, 127.21, 127.8
1, 128.34, 130.33, 132.10, 13
5.92, 136.42, 137.87, 142.3
It was 4, 158.48.

Synthesis Example 3. In the same manner as in Synthesis Example 2,
The compound represented by the following chemical formula 16 was obtained by reacting at a ratio of 4 / chemical formula 12 = 2/1.

[Chemical 16]

From the ultraviolet-visible absorption spectrum data,
The compound obtained was found to have a maximum absorption wavelength at 549 nm. The elemental analysis results show that the carbon atom content is 67.
58%, hydrogen atoms 7.33%, C ₁₂₀ H ₁₅₈ S
_There was good agreement with the respective calculated values for ₆ O ₆ Si ₉ , 67.84% and 7.31%.

Furthermore, ¹ HNMR (200 MH _Z , CDC
The measured value δ of l ₃ ) is 0.02 (s, 36H), 0.8
9 (s, 54H), 2.67 (br.s, 12H),
3.59 (br.s, 12H), 6.67 (d, J =
_{3.9H Z, 4H), 6.81 (} br.d, J = 2.7
_{H Z, 2H), 6.83-6.86 (} m, 6H), 7.
18 (dd, J = 1.0 and 5.1H _Z, 2H), 7.
28-7.48 (m, 18H), 7.64-7.74
(M, 12H);

The measured value δ of ¹³ CNMR (50 MH _Z , CDCl ₃ ) is −5.41, 18.36, 25.97, and 3.
6.25, 52.55, 65.40, 123.61, 1
24.27, 124.37, 124.64, 127.2
6, 127.36, 127.41, 128.28, 13
2.11, 132.19, 135.93, 136.7
It was 9, 142.15, 143.10, 158.36.

Synthesis Example 4. 1. To a dry hexane solution of 495 mg of the unsubstituted dithienylsilole (Chemical Formula 13) used in Synthesis Example 1, 0.4 ml of N, N, N ′, N′-tetramethylethylenediamine and 1.-n-butyllithium were added at room temperature.
1.6 ml of 67 mol hexane solution was sequentially added and stirred for 1 hour. Next, 0.81 ml of chlorotributyltin was dropped, and the mixture was further stirred for 1 hour, and 12 ml of a dry tetrahydrofuran solution containing 602 mg of dibromide (Chemical Formula 12) synthesized in Synthesis Example 1 and 52 mg of Cl ₂ Pd (PPh ₃ ) ₂ were added. .

The reaction mixture was stirred at 65 ° C. for one week, the solvent was distilled off, and the rest was dissolved in 50 ml of chloroform. The chloroform solution was washed twice with a 27 mM potassium cyanide aqueous solution and twice with water, and then dried over sodium sulfate. After filtration, the solvent was distilled off, the obtained solid was dissolved in a small amount of chloroform, reprecipitated with hexane, filtered, and washed with hexane to obtain 650 mg of a dark red-purple polymer represented by the following chemical formula 17. It was

[Chemical 17]

The weight average molecular weight was 12,600 and the number average molecular weight was 7,700. From the data of ultraviolet-visible absorption spectrum, the obtained compound was 594 nm and 615 nm.
It was found to have a maximum absorption wavelength in nm. The results of elemental analysis showed that carbon atoms were 64.61% and hydrogen atoms were 7.03%, and the calculated values for (C ₄₁ H ₅₂ O ₂ S ₂ Si ₃ ) _n were 67.90%. and 7.23%, and _{(C 4 H 9) 3 Sn} (C 41 H 52 O 2 S 2 Si 3) 10 Br
The respective calculated values for are 66.50% and 7.23%
Met.

Furthermore, ¹ HNMR (200 MH _Z , CDC
The measured value δ of l ₃ ) is 0.03 (s, 12H), 0.8
9 (s, 18H), 2.67 (s, 4H), 3.59
(S, 4H), 6.78 ( br.d, J = 3.7H Z,
2H), 6.88 (br.d, J = 3.7H Z, 2
H), 7.30-7.48 (m, 6H), 7.64-
7.76 (m, 4H); ¹³ C NMR (50M
The measured value δ of H _Z , CDCl ₃ ) is −5.43, 18.
34, 25.95, 36.31, 52.61, 65.3.
3, 123.62, 124.42, 127.42, 12
8.30, 130.26, 132.04, 135.8
7, 136.82, 142.10, 158.34.

Example 1 35 mg (0.138 mol) of Ni (acac) ₂ was dissolved in 1 ml of THF, then 41 μl (0.276 mmol) of PEt ₃ and DIBAH.
1 molar hexane solution (0.28 mL of DIBAH, which corresponds to 0.28 mmol) was added at room temperature and stirred for 30 minutes to prepare a nickel catalyst solution.

Next, the diyne of the following chemical formula 18, HMe ₂ Si
33 mg (0.276) of disilane represented by SiMe ₂ H
Mmol) and 3 ml of dry THF, the above nickel solution was added dropwise, and the mixture was stirred under reflux for 17 hours.

[Chemical 18] MPLC using silica gel (hexane / CH ₂ Cl ₂
= 5/1, Rf = 0.41),
92 mg (56 μmol) of a reddish purple solid TS′-TS′-TS′-T oligomer was obtained with a yield of 41%. The ultraviolet absorption maximum wavelength of the obtained oligomer is as shown in Table 1.

[0038]

[Table 1]

Examples 2-5. Applying the method of synthesis example,
H (-TS'T--) ₁₁ H (Example 2) and H (-T), respectively.
TS'T--) ₂₇ H (Example 3), H (-TTS'TT
-) ₄₁ H (Example 4) and H (-TST--) ₁₁ H (Example 5) were synthesized, and each was doped with iodine until the molecular weight, the maximum absorption wavelength of ultraviolet rays, and the conductivity became constant. The subsequent conductivity was measured. The results are as shown in Table 1 above. In addition, T represents thiophene, and S and S ′ are as shown in Chemical Formulas 19 and 20 below.

[0040]

[Chemical 19]

[Chemical 20] S ′ can be easily synthesized by intramolecular cyclization of the thiophene-containing diyne and dihydrotetramethylsilane used in the synthesis of TST using a nickel catalyst.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshiki Nakagawa 1-10-710 Kamigaharayamada-cho, Nishinomiya-shi, Hyogo

Claims (2)

[Claims] 1. A thiophene-silole copolymer represented by the following Chemical Formula 1; However, R in the chemical formula 1 is a monovalent hydrocarbon group having 1 to 7 carbon atoms or a hydrogen atom; A and B are an alkyl group, an aromatic group,
An alkenyl group or an aliphatic group in which A and B are combined to form a ring, m and p are integers of 1 or more, n is an integer of 0 or more, X is a hydrogen atom or a halogen atom, and Y is a hydrogen atom, It is a halogen atom or thiophene. 2. A compound represented by the following general formula 2 and a compound represented by the following general formula 3 are reacted in the presence of a nickel or palladium metal complex: A method for producing a thiophene-silole copolymer represented by Chemical Formula 4; In the formula, R is a monovalent hydrocarbon group having 1 to 7 carbon atoms or a hydrogen atom, A and B are an alkyl group, an aromatic group, an alkenyl group, or an aliphatic group in which A and B are bonded to form a ring. Represents a group, a and b are integers of 0 or more, X'is a halogen atom,
Y'is a halogen atom or a hydrogen atom; In the formula, R, A and B are the same as those in Chemical formula 2, c and d are integers of 0 or more, M is SnR ₃ , BX ₂ , MgX or ZnX, and M ¹ is SnR ₃ , BX ₂ , MgX, Zn
X or a hydrogen atom; R, A and B in the formula are the same as those in Chemical formula 2, X is a hydrogen atom or a halogen atom, Y is a hydrogen atom or a halogen atom or thiophene, m is a + c, n is b + d, and m and p are While being an integer of 1 or more, n is an integer of 0 or more.