JPH01172387A - Dipyrrolo(3,2-b:2',3'-d)pyrroles and production thereof - Google Patents

Abstract

NEW MATERIAL:Compounds expressed by formula I (R1-R3 are H, lower alkyl or aralkyl). EXAMPLE:4,7-Dihydro-1,4,7-trimethyl-1H-dipyrrolo[3,2-b:2',3'-d]pyrrole. USE:A raw material for electrical and electronic materials, physiologically active substance, such as medicines, agricultural chemicals, etc., and intermediate for production thereof. PREPARATION:2,6-Dialkoxycarbonyl-dipyrrolo[3,2-b:2',3'-d]pyrroles expressed by formula II (R4 and R5 are lower alkyl) are hydrolyzed with a base (e.g., sodium hydroxide) and deposited with an acid.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention provides a general formula (T) useful as a raw material for electrical and electronic materials or an intermediate for pharmaceuticals and agricultural chemicals (wherein R1, R2, and h are each a hydrogen atom) , represents a lower alkyl group or an aralkyl group) and a method for producing the same.

<Prior art and problems to be solved by the invention> Above -
Dipyrrolo (3,2-b: 2') shown in Arson (1)
, 3'-d) Pyrroles are compounds described at the end of the literature.

<Means for Solving the Problems> The present inventors have discovered that dipyrolo C3, which is represented by -arson (1),
2-b: 2', 3'-d) As a result of various studies on the production method of pyrroles, 2,6-dialkoxydicarponyludipyrrolo(
3,2-b: 2', 3''-d] We found a very convenient production route using pyrroles as starting materials, and the compounds can be used as raw materials for electrical and electronic materials, physiologically active substances such as medicines and agricultural chemicals, or as intermediates in their production. They discovered that it is useful for the body, and completed the present invention.

That is, the present invention provides divirolo(3,2-b: 2', 3' -d] virols, and 2,6-dialkoxycarponyl dipyrrolo(3,2-
b: 2', 3'-d) General formula (2', 3'-d) characterized by hydrolyzing pyrroles using a base and then acid precipitation (
1) (wherein Rls Rz and R1 represent the same meanings as above,
). Dipyrrolo (3,2-b:2″, 3′-d
) provides a method for producing pyrroles.

The compound targeted by the present invention is divirolo (3,2-b: 2', 3'-d) represented by -arson (I) above.
Specific examples of the substituents R3, R2, and R1 include a hydrogen atom, a lower alkyl group having 1 to 8 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, heptyl, and octyl, benzyl, Examples include aralkyl groups having 7 to 12 carbon atoms in total, such as tolylmethyl, phenylethyl, chlorophenylmethyl, phenylethyl, and phenylpropyl.

Examples of the substituents R4 and R2 in the general formula [■] which are the starting materials include lower alkyl groups having 1 to 8 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, heptyl, and octyl. The compound can be produced by the method described in Japanese Patent Application No. 118652/1988, previously proposed by the present inventors.

Next, the method of the present invention will be explained.

When the starting material compound (n) is hydrolyzed using a base, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is usually used as the base. The amount used is usually at least twice the molar amount of compound (n). The reaction temperature is generally 30 DEG C. to 120 DEG C., the reaction time is generally 1 to 30 hours, and alcohols such as methanol and ethanol are usually used as the reaction solvent. By precipitating the salt of carboxylic acid and base produced by hydrolysis, not only a neutralization reaction but also a decarboxylation reaction occur simultaneously, easily yielding the target compound dipyrrolo(3,2-b:2').

3''-d) Pyrrole H[+] is produced.The acid used for acid precipitation is usually a mineral acid such as sulfuric acid or hydrochloric acid.The zero reaction is sufficient even at room temperature, and upon contact with the acid, The product, dipyrrolo(3,2-b:2
°, 3'-d] Viroles CI) can also be purified by a suitable method, such as column chromatography.

In this way, the compound of the present invention represented by -arson (1) is obtained, and the compound of the present invention can be a useful raw material for electrical and electronic materials. It can also be used as a physiologically active substance for medicines and agricultural chemicals or as an intermediate thereof.

For example, a polymer obtained by electrolytically polymerizing the compound of the present invention can be a conductive polymer. In addition, the compounds of the present invention have the advantage that they can be polymerized at lower potentials than pyrrolo(3,2-b)pyrroles, and the electrochemical doping of the resulting polymers can also be carried out at lower potentials. have

The electrolytic solution used in electrolytic polymerization can be prepared by dissolving the compound of the present invention (hereinafter abbreviated as monomer) and supporting electrolyte in a suitable solvent.

The supporting electrolyte may be one that is stable at the polymerization potential of the monomer, and examples thereof include metal salts containing perhalogenate ions, boron halide ions, phosphorus halide ions, organic sulfonate ions, or quaternary ammonium ions. I can give you some salt. A specific example of these is Li
Cl0n, LiBF4゜NaClO4, KCl041
NaBF, (n-Bu) pH' Cl041 Na
PFblLiPF,, CH3 building 5OJa+ (Et)a
N-BF4. (Et)aN-PF6 and the like can be mentioned.

Examples of solvents include, but are not limited to, acetonitrile, γ
-Butyrolactone, tetrahydrofuran, benzonitrile, nitrobenzene, etc. are effectively used.

The monomer concentration in the electrolytic solution should be at or below the saturation concentration, but if it is too low, side reactions such as decomposition of the solvent and electrolyte are likely to occur during electrolytic oxidation polymerization, and bonding reactions between electrolytically generated active species are difficult to occur. Therefore, a concentration of 0.001 mol/2 or more is usually preferable.

The concentration of the supporting electrolyte is also not particularly limited, but if the concentration is too low, the resistance of the electrolyte increases, so it is used at a concentration of 0.01 mol/1 or more and below the saturation concentration.

The temperature during electrolytic oxidation polymerization is within the range where the electrolyte is in a solution state,
That is, it can be carried out at a temperature above the solid point and below the boiling point, but usually from 0°C to 100'C, preferably from 10°C to 70°C.
is within the range of

The electrode material to be used is not particularly limited as long as it is stable under the electrolytic oxidation polymerization conditions and has an electrical conductivity of 10-'S/a+ or higher. Usually, platinum, gold, graphite, tin oxide, isodium oxide-tin oxide ( ITO) etc. are used. These can be used alone, in the form of a support on glass or resin film, or in the form of a composite.

Further, it is preferable that the electrolytic oxidative polymerization is performed in an atmosphere of an inert gas such as nitrogen or argon.

As the electrochemical oxidative polymerization method, commonly used methods can be used. For example, a constant current method, a constant potential method, a constant voltage method,
Potential sweep method, potential step method and alternating current method can be mentioned.

By the above method, dipyrrolo[3,2-b: 2',
3'-d) A polymer of pyrroles can be obtained.

Note that this polymer usually incorporates electrolyte ions used as a supporting electrolyte.

The resulting dipyrrolo(3,2-b: 2', 3'-d
) Pyrrole polymers are obtained in the form of black, extremely smooth films, and another great advantage is that when using constant potential electrolysis or constant current electrolysis, the film thickness can be controlled in proportion to the amount of electricity required for polymerization. .

The film thus produced exhibits semiconductivity, but its conductivity can be further increased by further chemical doping, electrochemical doping, or ion implantation.

Furthermore, since this polymer membrane can be electrochemically doped and undoped in an electrolyte, it can be applied to electrode materials for secondary batteries, sensors using modified electrodes, electronic devices, etc. It has great industrial value as an electronic material.

<Effects of the Invention> The compound (T) of the present invention is a compound containing 14π electrons that has not been described in any literature, and can be a useful raw material for electrical and electronic materials. In addition, the compounds of the present invention can be used as physiologically active substances for pharmaceuticals and agricultural chemicals,
Or it can be an intermediate thereof.

In addition, according to the method of the present invention, the decarboxylation reaction can proceed by a simple operation of hydrolyzing compound (n) with a base and then precipitating it with acid, and the target compound (1) can be easily obtained. (3,2-b: 2″, 3″-d) This is a moderate method for industrially producing virols.

<Examples> Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited only to these Examples.

Example 16 Preparation of 4,7-sihydro1,4,7-trimethyl-LH-dipyrrolo(3,2-b:2',3'-d)pyrrole.

4°7 of 2,6-dicarboethoxy in 20d of ethanol
-Sihydro1.4.7-)limethyl-IH-dipyrrolo(3,2-b: 2', 3'-d)pyrrole 20
0 mg (0,6042 mmol) and 1.2084 g (3,021 mmol) of 10% sodium hydroxide were added, and the mixture was reacted under heating under reflux for 20 hours.

After the reaction, ethanol was concentrated under reduced pressure, and 50 ml of water and 50 ml of diethyl ether were added to the residue. After shaking, diethyl ether was separated and removed. In the aqueous layer, lN-1 (CI is P
Acid precipitation was performed by adding up to H-7. After extraction twice with chloroform 30d, the chloroform layer was washed with saturated saline and separated.

After drying the chloroform layer over anhydrous sodium sulfate, the chloroform was concentrated under reduced pressure to give 38.5111 g (yield 34.
1%) of a green solid was obtained. Purification was performed by column chromatography (silica gel, chloroform elution) to obtain a pale green solid.

Melting point 144-147°C Elemental analysis (C++ HI3N5) HN Calculated value (%) ? 0.59 6.95 22.46 Actual value (%') 70.51 6.97 22.32 Mass analysis IIl/e 187 (M") IR (KBr) 3450, 2920.1510.1408.1358
cm-''H-NMR (90MHz, δ'jjL
'+TMS) 3.59 (3H,S), 3.84
(6H,S)5.95 (2H,d, J-2,7
Hz) 6.43 (2H, d, J-2,7Hz)
Reference example 1 2-carboethoxy-1,4-dihydro-1,4-dimethyl-5-formyl-pyrrolo[3,2-b゛]]virol preparation example (1-1) 2-azido-3-(1 Preparation of -methyl-5=pormyl-IH-pyrrol-2-yl)-ethyl acrylate Dimethylformamide 5d was cooled to 0 to 5°C under nitrogen atmosphere. Here 1.075 g of phosphorus heoxychloride (7,
015 mmol) was added with stirring, and the mixture was stirred at the same temperature under a nitrogen atmosphere for 30 minutes. 2-Azide-3 is added to the resulting solution.
-(1-Methyl-IH-pyrrol-2-yl)-ethyl acrylate (0.772 g (3,508 mmol)) was added dropwise in dimethylformamide, and the mixture was stirred at 0 to 5°C for 30 minutes. The temperature was further raised to room temperature and stirred for 6 hours.

After the reaction, 100 d of water was added and neutralized with 10% sodium hydroxide. The precipitated solid was separated by filtration, washed with water, and then dissolved in chloroform. The chloroform solution was dried and then concentrated under reduced pressure to obtain 0.5760 g of yellow crystals.

This was purified by column chromatography to obtain 0.5432 g (yield 62%) of yellow crystals of ethyl 2-azido-3-(1-methyl-5-formyl-IH-pyrrol-2-yl)-acrylate. Ta.

Melting point 87-89°C Calculated value (%) 53.2 4.8 22.6 Actual value (%) 52.6 4.9 22.11R
(KBr) 3450, 2120, 1720. 1670cm
Kan'H-NMR (90MHz, δCl)j13
) 1, 40 (3H, t), 4.00 (3H,
s) 4, 36 (2H. q), 6.81 (11 (
, s) 6,95 (18, d. J=3.3Hz)
7, 15 (IH, d, J=3.3Hz) 9, 70
(1) 1, s) (1-2) Production of 2-carboethoxy-1,4-dihydro-4-methyl-5-formyl-pyrrolo(3,2-b)virol.

In p-xylene 380-ethyl 2-azido-3-(1-methyl-5-formyl-IH-pyrrol-2-yl)-acrylate obtained in the same manner as (1-1)8.
87 g (35, fromimole) was added and dissolved. This solution was heated under reflux for 10 minutes under a nitrogen atmosphere.

After cooling, the solvent was concentrated under reduced pressure to obtain brown crystals.

4.84 g of 2-carboethoxy-1,4-dihydro-4-methyl-5-formyl-pyrrolo(3,2-b
) Light brown crystals of pyrrole were obtained. Yield 61%, melting point 11
6~118°C Calculated value (%) 60.0 5.5 12.7 Actual value (%) '60.2 5.5 12.5IR (KB
r) 3320, 1690.1665.1300 Cl1-'
'H-NMR (90M) Iz, 6 cFi',''
)1.40 (3H,t), 4.00 (3H
, s) 4.36 (2H, q), 6.60 (
18,s) 6.69 <IH,s), 8.70
(Ifl, b)9.56 (IH,5) (1-3) 2-carboethoxy-1,4-dihydro-1,4-dimethyl-5-formyl-pyrrolo[3°2-
b] Production of virol.

2- obtained in (1-2) in 7.8 g of dimethylformamide
Carboethoxy-1,4-dihydro-4-methyl-5-
Formyl-pyrrolo(3,2-b)pyrrole 0.543
1 g (2,4686 mmol), anhydrous potassium carbonate 1
．． 666 g (12,073 mmol) and 1.8658 g (13,1397 mmol) of methyl iodide were added, and the mixture was stirred at room temperature under a nitrogen atmosphere for 3 hours.

After the reaction, 100 s of water and 100 s of diethyl ether were added to separate the liquids. The aqueous layer was extracted with diethyl ether (30
dx2) and combined with the organic layer. The organic layer was washed with saturated brine, dried and concentrated under reduced pressure. By purifying the obtained crystals with column chromatography, 0.5485 g of 2-
Pale yellow crystals of carboethoxy-1,4-dihydro-1,4-dimethyl-5-formyl-pyrrolo[3°2-b]pyrrole were obtained. Yield 95%, melting point 98-101"C Calculated value (%) 61.5 6.0 11.9 Actual value (%) 61.4 6.0 11.8IR (KBr
) 3480, 1720.16B0.1410.1230
cm-''H-NMR (90MHz, δC
■Muko) 1.39 (3H, t), 3.95 (3
H, s) 3.96 (3H, s), 4.33 (2H
,q)6.56 (LH,s), 6.69 (18,
s) 9.57 (11(,s) Reference Example 2 (2-1) 2-azido-3-(2-carboethoxy-1,4-dihydro-1,4-dimethyl-pyrrolo(3,
2-b) Production of ethyl pyrrol-5-yl)acrylate.

0.4914 g (21,3675 mmol) of metallic sodium was added and dissolved in dry ethanol (20d) under a nitrogen atmosphere. The resulting solution was cooled to -30'C and 1.0 g of 2-carboethoxy-1,4-dihydro-1,4-dimethyl-5-formyl-pyrrolo(3,2-b)pyrrole (4,2735 A diethyl ether solution (20 sffi) of 2.7564 g (21,3675 mmol) of ethyl azide and ethyl azide was added dropwise over 10 minutes. After stirring at -30'C for 5 hours, the temperature was raised to room temperature.

After the reaction, 250ml of water! and diethyl ether 300 were added to separate the layers. The aqueous layer was extracted with diethyl ether (5
After washing the organic layer and the organic layer with saturated saline, the organic layer was dried and condensed under reduced pressure. The obtained crystals were recrystallized from diethyl ether/n-hexane (20/80) to give 0.7793 g of 2-azido-3-(2-
Yellow crystals of ethyl carboethoxy-1,4-dihydro-1,4-dimethyl-pyrrolo(3,2-bl pyrrol-5-yl)-acrylate were obtained.

Yield 53%, melting point 118-120°C Calculated value (%) 55.6 5.5 20.3 Actual value (%) 55.8 5.6 19.7IR (KBr
) 3450.2140.1705 cm -''I(-
NMR (90M)+2, δ(FjLj)1.37
(31(,t)+1.39 (3)1.
t) 3.66 (3H,s), 3.95 (3
M, s) 4.30 (28,q), 4.36
(2H, q) 6.67 (LH, s) 6.9
3 (IH,s)6.97 (IH,5) (2-2) 2.6-dicarboethoxy4.7-sihydro4.7-dimethyl-IH-divirolo[3,2-
bl', 3'-d) Production of pyrrole.

2-azido-3-(2-carboethoxy-1,
4-dihydro-1,4-dimethyl-pyrrolo[3,2-1
))H-o-5-yl)ethyl acrylate l.

Og (2,8985 mmol) was added and dissolved. The solution was heated to reflux under nitrogen atmosphere for 10 minutes.

After cooling, 150% of n-hexane was added and the precipitated white crystals were collected by filtration. The obtained crystals were dried to give 0.6883 g of 2,6-dicarboethoxy 4,7-dihydro 4,7
-Simethyl-IH-divirolo(3,2-b:2',3'
-d) Pyrrole was obtained.

Yield 75%, white crystals, melting point 102-105°C Calculated value (%) 60.5 6.0 13.2 Actual value (%)
60.6 6.1 13.1 Mass analysis m/e
317 (M”) IR (KBr) 3450, 1700 cm-K'4141-1l (90M)lz, δl:j几2
) 1.37 (3H, D, 1.38 (3n, t)
3.60 (3H,S), 4.14 (3H,s)4
．． 32 (2H, q), 4.36 (2H, q)6.
74 (21(,S), 9.10 (IH,b) Reference Example 3 2.6-dicarboethoxy 4.7-dihydro 1,4
．． 7-) Limethyl-IH-divirolo(3,2-b:2
', 3''-d] Production example of pyrrole 1.0 g (13,6980 mmol) of dimethylformamide was added with 4.7 2,6-dicarboethoxy-4,7-sihydro obtained in Reference Example (2-2) -Simethyl-IH-
Dipyrrolo(3,2-b:2',3'-d)virol 70 g (0,2208 mmol), anhydrous potassium carbonate O, 1492 g (1,0798 mmol) and methyl iodide 0.1669 g (1 , 1752 mmol) and stirred at room temperature for 5 hours under a nitrogen atmosphere.

After the reaction, 101d of water and 10-diethyl ether were added to separate the mixture. The aqueous layer was extracted with diethyl ether (10dX
2 times) combined with the organic layer. The organic layer was washed with saturated brine, dried and concentrated under reduced pressure. The obtained crystals were purified by column chromatography to obtain 60.6 ffg of 2,6-dicarboethoxy-4,7-sihydro-1,4,7-trimethyl-IH.
- Crystals of divirolo[3,2-b:2',3'-d]pyrrole were obtained.

Yield 83.0%, colorless crystals, melting point 156-158°C Actual value (%) 616 6.5 12.3 Mass analysis
m/e 331 (M”) IR (XBr) 3440, 1700 cm −1 'H-NMR (90M! (z, δc elbow L3) 1.
37 (6H,t), 3.57 (38,s)
4.26 (6H,S), 4.30 (4L
q>6.75 (2H,s) Reference Example 4 Monomer 4,7-sihydro1.4.7-trimethyl-LH-dipyrrolo[3,2-b: 2', 3
°-d) 3.5 mmol/1 virol and 0.5 mmol/1 LiCl as supporting salt. An acetonitrile solution containing 200 mmol/l of! This is the solution.

A PT plate was used as a working electrode and a counter electrode, and a silver/silver chloride electrode was used as a reference electrode. In an Ar atmosphere, the voltage between the working electrode and the reference electrode is between -0.6V and +0.5V at 50mV/s.
Electrolytic polymerization was performed at room temperature by sweeping the potential at a sweep rate of ec.

From the first sweep, an anode current having a peak at 0.1 V with respect to the reference electrode was observed, and formation of a black film-like substance was observed on the working electrode. After 15 minutes of electrolytic polymerization, the working electrode with the polymer film attached was taken out and placed in a 200 m tube containing no monomer.
It was placed in an acetonitrile solution containing mol/Il of LiCIO4 as a supporting salt. Using a PT plate as the counter electrode and a silver/silver chloride electrode as the reference electrode, -
50mV/sec between 0.8V and +0.4V T:
A potential sweep was performed. An anode current and a cathode current corresponding to doping and dedoping of CIO, - were observed, and the half-wave potential thereof was -0.2v vs Ag/AgCl.

Furthermore, the integrated values of the anode current and cathode current showed that doping and dedoping occurred reversibly.

Reference Example 5 A polymer film prepared in the same manner as in Reference Example 4 was taken out while still attached to the PT plate. LIC104-20 as a supporting salt
Propylene carbonate containing 0 mmol/1 was used as the electrolyte, and Li pieces were used as the counter and reference electrodes.
A sec potential sweep was performed. Anode current and cathode current corresponding to ClO4- doping and dedoping are observed, and the half-wave potential is 2.8V vs Li /
It was Li゛. Furthermore, the integrated values of the anode current and cathode current showed that doping and dedoping occurred reversibly.

Reference Example 6 Electrolytic polymerization was carried out in the same manner as in Reference Example 4 except that a glass plate with ITO was used as the working electrode to obtain a black polymer film. When the surface of this film was observed with a scanning electron microscope, it was found to be extremely smooth.

Reference Example 7 1,4-dihydro-1,4 dimethyl-L as a 7-mer
Electrolytic polymerization was carried out in the same manner as in Reference Example 4 except that H-pyrrolo(3,2-b)pyrrole was used. 0.5ν relative to reference pole
An anode current with a peak was observed, and a black film-like substance was observed to form on the working electrode.

When a potential sweep was performed in the same manner as in Reference Example 5 in an electrolytic solution containing no monomer, the half-wave potential corresponding to doping and dedoping was 3.3 V vs. Li/Li''.

Claims (2)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, R_1, R_2, R_3 are hydrogen atoms,
Represents a lower alkyl group or an aralkyl group. ) Dipyrrolo[3,2-b:2',3'-d]pyrroles represented by: (2) General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (In the formula, R_1, R_2, R_3 are hydrogen atoms,
Represents a lower alkyl group or an aralkyl group, R_4,
R_5 each represents a lower alkyl group. ) A general formula characterized in that 2,6-dialkoxycarbonyl-dipyrrolo[3,2-b:2',3'-d]pyrroles represented by the formula are hydrolyzed using a base and then precipitated with acid. [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, R_1, R_2, R_3 represent the same meanings as above.) Dipyrrolo[3,2-b:2',3' −
d] Method for producing pyrroles.