KR20020067659A - Benzodioxinopyrroles, Their Preparation and Use - Google Patents

Abstract

PURPOSE: Provided are substituted or unsubstituted benzodioxinopyrroles and their preparation. Further provided is the use of the substituted or unsubstituted benzodioxinopyrroles for preparing electrically conductive oligomers or polymers and oligomers or polymers which comprises these pyrrole derivatives as repeating unit. CONSTITUTION: The substituted or unsubstituted benzodioxinopyrroles of the formula(1) are prepared by reaction of a substituted 1,2-dihydroxypyrrole with a 1,2-difluorobenzene and subsequent saponification and decarboxylation of the intermediate formed.

Description

Benzodioxinopyrroles, Methods of Making and Uses thereof {Benzodioxinopyrroles, Their Preparation and Use}

The present invention relates to substituted or unsubstituted benzodioxynopyrroles (hereinafter referred to as 3,4- (1,2-benzodioxy) -pyrrole), methods for their preparation and their use for the preparation of electrically conductive oligomers or polymers. It is about. The present invention also relates to oligomers or polymers comprising the compounds as repeat units.

Conductive organic polymers have been widely applied. One example that may be mentioned is the use of such polymers in the manufacture of polymer batteries, diodes or transistors, or solar cells. As the conductive organic polymer, for example, systems based on polyacetylene, poly (p-phenylene), polythiophene or polypyrrole are used. The advantage of polypyrrole over other conductive polymers is that polypyrrole can be obtained directly from the synthesis in doped form, which is also stable under ambient conditions (Roempp Lexikon Chemie, Version 2.0, Stuttgart / New York, Georg Thieme Verlag). 1999, "Polypyrrole").

Several electrically conductive oligomers and polymers are known that can be prepared from pyrrole derivatives. Specific examples are commercially available polypyrrole itself. For example, there is a conductive polymer sold by DSM under the trade name ConQuest®. They are based on thermoplastic polyurethane particles coated with polypyrrole. Synthesis of 3-phenylpyrrole is described by Tetrahedron Lett. (1984), 25 (16), 1659-60. Synth. Met. (1990), 38 (3), 371-379, disclose that 3-phenylpyrrole and 3-propanoylpyrrole can be electrochemically polymerized. In addition, polymers of arylpyrrole and aryloxypyrrole are described in EP 261 837 A2. In the polymers of arylpyrrole and aryloxypyrrole, aryl substituents are simple phenyl, tolyl or naphthyl radicals, and aryloxy substituents are phenoxy, methylphenoxy and naphthoxy radicals. The polymer is obtained from these pyrrole derivatives by reacting with a specific oxidant comprising at least one copper compound and at least one nitrile compound. 3,4-benzodioxy substituted polypyrroles have not been previously known.

In order to be able to meet the respective requirements of the desired degree of properties of the polymer, it is necessary to have a number of suitable monomer building blocks available. It is therefore an object of the present invention to provide novel pyrrole derivatives and to find methods for their preparation.

Finally, new pyrrole derivatives can be prepared. These are substituted or unsubstituted 3,4- (1,2-benzodioxy) -pyrrole. These compounds may have a wide variety of distinct substituents that can affect their electrical structure to the desired extent, which is of particular interest as monomers for producing conductive polymers.

Accordingly, the present invention provides a compound of formula 1 below.

Where

R ¹ and R ² are each independently of each other H, C ₁ -C ₂₀ -alkyl, C ₆ -C ₁₀ -aryl, C ₇ -C ₁₂ -aralkyl, C ₁ -C ₁₈ -alkoxy, C ₂ -C ₁₈ -Hydroxyalkyleneoxy, C ₂ -C ₃₆ -alkoxyalkyleneoxy, hydroxyethyl, formyl, C ₂ -C ₁₈ -acyl, nitro, halogen, sulfo, cyano, carboxy, C ₁ -C _18- Alkoxycarbonyl or trifluoromethyl or together with the aromatic ring to which they are attached form an fused aromatic ring system,

R ³ represents H, C ₁ -C ₁₈ -alkoxycarbonyl, propylsulfonyl, butylsulfonyl, C ₁ -C ₂₀ -alkyl, C ₆ -C ₁₀ -aryl or C ₇ -C ₁₂ -aralkyl.

R ¹ and R ² are preferably each independently of each other H, C ₁ -C ₁₈ -alkyl, benzyl, C ₁ -C ₁₈ -alkoxy, C ₂ -C ₄ -acyl, nitro, halogen, for example fluorine, Chlorine or bromine, sulfo (SO ₃ H), cyano (CN), carboxy (COOH) or C ₁ -C ₁₈ -alkoxycarbonyl, particularly preferably H, cyano, carboxy or C ₁ -C ₄ -alkoxy Carbonyl. Very particular preference is given to at least one radical R ¹ and R ² being hydrogen.

Preferably, when the positions of the O substituents are 1 and 2, R ¹ is positioned at 4 position of the aryl ring, and R ² is positioned at position 5 of the aryl ring.

R ³ preferably denotes H, tert-butoxycarbonyl, C ₁ -C ₁₈ -alkyl or benzyl, particularly preferably H or benzyl.

Compounds of formula (1) can be prepared, for example, by reacting a suitable dihydroxypyrrole with difluorobenzene substituted with a nucleophilic aromatic substituent by nucleophilic aromatic substitution (Eastmond, GC) and papprotney. Synthesis based on the method of Paprotny, J. (Chem. Lett. 6 (1999), 479-480).

Accordingly, the present invention also reacts the dihydroxypyrrole of formula (2) with difluorobenzene of formula (3) to obtain a compound of formula (4), followed by saponification and decarboxylation of the compound of formula (4) Provided is a method of preparing the compound of 1.

Where

R ¹ and R ² are each independently of each other H, C ₁ -C ₂₀ -alkyl, C ₆ -C ₁₀ -aryl, C ₇ -C ₁₂ -aralkyl, C ₁ -C ₁₈ -alkoxy, C ₂ -C ₁₈ -Hydroxyalkyleneoxy, C ₂ -C ₃₆ -alkoxyalkyleneoxy, hydroxyethyl, formyl, C ₂ -C ₁₈ -acyl, nitro, halogen, sulfo, cyano, carboxy, C ₁ -C _18- Alkoxycarbonyl or trifluoromethyl or together with the aromatic ring to which they are attached form an fused aromatic ring system,

R ^{3 ′} represents C ₁ -C ₁₈ -alkoxycarbonyl, propylsulfonyl, butylsulfonyl, C ₁ -C ₂₀ -alkyl, C ₆ -C ₁₀ -aryl or C ₇ -C ₁₂ -aralkyl,

R ^{4 ′} represents C ₁ -C ₁₈ -alkyl.

The reaction of dihydroxypyrrole of formula (2) with difluorobenzene of formula (3) is, for example, in a bipolar aprotic solvent in the presence of a base such as potassium carbonate under protective gas atmosphere (Ar, N ₂ ) at atmospheric pressure. Can be performed.

Suitable solvents are, for example, dimethylformamide, dimethylacetamide, dimethyl sulfoxide and high boiling ketones. Preference is given to using dimethylformamide as the solvent.

The reaction can be carried out, for example, at a temperature of 100 to 160 ° C, preferably 120 to 140 ° C.

In order to prepare compounds of formula 1 wherein R ³ is hydrogen, further dealkylation has to be carried out. The dealkylation can be carried out, for example, after reacting dihydroxypyrrole of formula (2) with difluorobenzene of formula (3) and before saponifying and decarboxylation of the compound of formula (4).

Dealkylation can be carried out under generally customary conditions for such reactions. For example, the compound of formula 4 can be heated in a mixture of trifluoroacetic acid and sulfuric acid.

Likewise, saponification can also be carried out under conditions customary for such reactions. For example, if after dealkylation is appropriate, the compound of formula 4 may be heated in dilute aqueous sodium hydroxide or potassium hydroxide, and then the reaction mixture is neutralized with hydrochloric acid or sulfuric acid.

Decarboxylation can also be carried out by methods known per se. For example, saponification of the compound of formula 4, followed by high temperature in ethanolamine or in a bipolar aprotic solvent such as dimethylacetamide or dimethyl sulfoxide in the presence of a catalyst such as basic copper carbonate or copper chromoline quinoline, For example, it is heated to 160-200 degreeC.

In addition, compounds of formula (1) wherein R ¹ and R ² are each hydrogen, for example, react dihydroxypyrrole of formula (2) with, for example, 2-chloronitrobenzene or 2-fluoronitrobenzene and Lee, HH) and Denny, WA (synthesized based on J. Chem. Soc. Perkin Trans. I (1990), 1071-1074), followed by saponification and decarboxylation. have.

The compounds of formula 1 are also prepared by reacting, for example, 3,4-dialkoxypyrrole, preferably known 3,4-dimethoxypyrrole with substituted or unsubstituted 1,2-dihydroxybenzene can do. The reaction can be carried out, for example, in an aromatic solvent such as toluene or xylene in the presence of an acid catalyst such as sulfuric acid or p-toluenesulfonic acid under atmospheric pressure at 100 to 160 ° C., preferably at reflux.

The compound of formula 1 may be used for the preparation of an electrically conductive polymer. In the present specification, only one compound of formula 1 may be used as a monomer, or a mixture of various compounds of formula 1 corresponding to the definition of formula 1 may be used. It is also possible to add further pyrrole derivatives, in particular pyrrole itself, in addition to at least one compound of the formula (1) as monomer.

The polymerization is carried out in a similar manner to the polymerization of known pyrrole derivatives. The polymerization can be effected, for example, by an oxidation reaction using an oxidizing agent such as iron (III) chloride or other iron (III) salts, H ₂ O ₂ , sodium or potassium peroxosulfate, potassium dichromate, potassium permanganate, or electrochemical reactions. Can be done by

Accordingly, the present invention also provides the use of a compound of formula 1 for preparing an electrically conductive polymer and provides an electrically conductive polymer made by polymerization of a compound of formula 1.

In particular, the present invention provides an electrically conductive polymer of the formula (5).

Where

R ¹ and R ² are each independently of each other H, C ₁ -C ₂₀ -alkyl, C ₆ -C ₁₀ -aryl, C ₇ -C ₁₂ -aralkyl, C ₁ -C ₁₈ -alkoxy, C ₂ -C ₁₈ -Hydroxyalkyleneoxy, C ₂ -C ₃₆ -alkoxyalkyleneoxy, hydroxyethyl, formyl, C ₂ -C ₁₈ -acyl, nitro, halogen, sulfo, cyano, carboxy, C ₁ -C _18- Alkoxycarbonyl or trifluoromethyl or together with the aromatic ring to which they are attached form an fused aromatic ring system,

R ^{3 ''} represents H,

n represents the integer of 3-100.

R ¹ and R ² are preferably each independently of each other H, C ₁ -C ₁₈ -alkyl, benzyl, C ₁ -C ₁₈ -alkoxy, C ₂ -C ₄ -acyl, nitro, halogen, for example fluorine, Chlorine or bromine, sulfo (SO ₃ H), cyano (CN), carboxy (COOH) or C ₁ -C ₁₈ -alkoxycarbonyl, particularly preferably H, cyano, carboxy or C ₁ -C ₄ -alkoxy Carbonyl. Very particular preference is given to at least one radical R ¹ and R ² being hydrogen.

When the positions of the O substituents are set to 1 and 2, it is preferable that R ¹ is located at position 4 of the aryl ring and R ² is located at position 5 of the aryl ring.

n preferably represents an integer of 3 to 50, particularly preferably 4 to 15.

The above-mentioned compound of formula 4 is an intermediate for preparing the compound of formula 1. These intermediates are also novel.

Accordingly, the present invention also provides a compound of formula (4).

<Formula 4>

Wherein R ¹ , R ² , R ^{3 '} and R ^4' are as defined above.

The invention is illustrated below by way of examples, which are not intended to limit the scope of the invention.

<Example>

Example 1

<Step 1>

103 g (0.77 mol) of imino diacetic acid (1) were dissolved in 250 ml of anhydrous methanol. 200 ml of BF ₃ (CH ₃ OH) ₂ was added dropwise from the dropping funnel over 20 minutes. The reaction mixture was refluxed at 80 ° C for 14 h. After cooling, the mixture was introduced into 1.5 L of saturated aqueous sodium hydrogen carbonate solution, and solid sodium hydrogen carbonate was slightly added for a certain time until the pH reached 7.5. The mixture was then extracted twice with 1.5 L of chloroform and once with 2.5 L of chloroform. The chloroform phases were combined, dried over magnesium sulfate and evaporated on a rotary evaporator.

Yield: 121.5 g (98% of theory)

<Step 2>

110 g (0.68 mol) of compound (2), 114 g (1.37 mol) of sodium hydrogen carbonate and 116.7 g (0.68 mol) of benzyl bromide were dissolved in 300 ml of anhydrous DMF and heated at 40 ° C. for 17 hours. The cooled reaction mixture was extracted four times with 100 ml of toluene each time, the toluene phases were combined and washed twice with 200 ml of water each time. The toluene phase was dried over magnesium sulfate and evaporated on a rotary evaporator.

Yield: 134.4 g (78% of theory)

<Step 3>

59.4 g (1.1 mol) of sodium methoxide were dissolved in 250 ml of anhydrous methanol and mixed with 130 g (0.52 mol) of compound (3) and 61.1 g (0.52 mol) of dimethyl oxalate. The reaction mixture was refluxed for 12 hours. After cooling, the reaction mixture was adjusted to pH 5 with glacial acetic acid and poured into 500 ml of ice water. The precipitated solid was filtered off, washed with water, dried under reduced pressure and recrystallized from acetone.

Yield: 103 g (65% of theory)

<Step 4>

3.39 g (0.011 mol) of compound (4), 1.9 g (0.011 mol) of 3,4-difluorobenzonitrile and 1.54 g (0.011 mol) of potassium carbonate were dissolved in 50 ml of anhydrous DMF under an argon atmosphere, and 15 at 130 ° C. Heated for hours. After cooling the reaction mixture, the contents of the flask was poured onto 200 ml of ice / water mixture, the solids were filtered off, washed twice with 150 ml of water and dried at 40 ° C. under reduced pressure. Then it was recrystallized from acetonitrile.

Yield: 4.23 g (95% of theory)

Mass spectroscopy: theory: M ⁺ = 404.37

Found: (FD-MS) m / e = 404.7 (Intensity: 100%)

Elemental analysis: Theory: C 65.34, H 3.99, N 6.93

Found: C 65.72, H 3.99, N 7.10

Example 2

1 g (0.0025 mol) of compound (5) was dissolved in 3 ml of trifluoroacetic acid and 0.1 ml of H ₂ SO ₄ (adding 0.35 g of anisole) and heated at 90 ° C. for 35 minutes. Trifluoroacetic acid was then distilled off under reduced pressure. The residue was cooled in an ice bath, mixed with 15 ml of methylene chloride, neutralized with saturated sodium hydrogen carbonate solution and extracted three times with 100 ml of methylene chloride. The methylene chloride phase was evaporated and the residue was recrystallized from methanol.

Yield: 0.39 g (50% of theory)

Mass Spectroscopy: Theory: M ⁺ = 314.25

Found: (FD-MS) m / e = 314.6 (Strength: 30%)

Example 3

0.2 g of compound (6) was heated in 55 ml of 2N NaOH for 30 minutes at 95 ° C. After cooling, the mixture was adjusted to pH 2 with hydrochloric acid. The aqueous phase was extracted with diethyl ether (5x100 ml) and evaporated on a rotary evaporator.

Yield: 95% of theory

Mass Spectroscopy: Theory: M ⁺ = 305.20

Found: (FD-MS) m / e = 305.5 (Intensity: 53%)

Found: 261.5 (M ⁺ -CO ₂ ) (Strength: 7%)

Found: 217.5 (M ⁺ -2CO ₂ ) (Strength: 33%)

Example 4

99 mg of compound (7) was dissolved in 20 ml of ethanolamine and heated to 180 ° C. for 45 minutes under argon atmosphere.

Yield: about 90% (evaluated by FD-MS)

Mass Spectroscopy: Theory: M ⁺ = 217.18

Found: (FD-MS) m / e = 217.5 (Intensity: 90%)

Found: 260.7 (Strength: 10%)

The second peak is attributable to ethanolamide of compound (8) when referring to compound (9) below.

According to the present invention, substituted dihydroxypyrrole is reacted with difluorobenzene to obtain an intermediate, which is then saponified and decarboxylated to prepare a substituted or unsubstituted benzodioxynopyrrole. Such substituted or unsubstituted benzodioxynopyrroles can be used in the production of conductive oligomers or polymers, and oligomers or polymers comprising the pyrrole derivatives as repeating units can be prepared.

Claims (10)

A compound of formula 1 <Formula 1> Where R ¹ and R ² are each independently of each other H, C ₁ -C ₂₀ -alkyl, C ₆ -C ₁₀ -aryl, C ₇ -C ₁₂ -aralkyl, C ₁ -C ₁₈ -alkoxy, C ₂ -C ₁₈ -Hydroxyalkyleneoxy, C ₂ -C ₃₆ -alkoxyalkyleneoxy, hydroxyethyl, formyl, C ₂ -C ₁₈ -acyl, nitro, halogen, sulfo, cyano, carboxy, C ₁ -C _18- Alkoxycarbonyl or trifluoromethyl or together with the aromatic ring to which they are attached form an fused aromatic ring system, R ³ represents H, C ₁ -C ₁₈ -alkoxycarbonyl, propylsulfonyl, butylsulfonyl, C ₁ -C ₂₀ -alkyl, C ₆ -C ₁₀ -aryl or C ₇ -C ₁₂ -aralkyl. The compound of claim 1, wherein R ¹ and R ² are each independently of each other H, C ₁ -C ₁₈ -alkyl, benzyl, C ₁ -C ₁₈ -alkoxy, C ₂ -C ₄ -acyl, nitro, halogen, sulfo, A cyano, carboxy or C ₁ -C ₁₈ -alkoxycarbonyl. The compound of claim 2, wherein R ¹ and R ² are each independently of each other H, cyano, carboxy, or C ₁ -C ₄ -alkoxycarbonyl. 2. The compound of claim 1, wherein when the positions of the O substituents are set at positions 1 and 2, R ¹ is located at position 4 of the aryl ring and R ² is located at position 5 of the aryl ring. The compound of any one of claims 1-4, wherein R ³ represents H, tert-butoxycarbonyl, C ₁ -C ₁₈ -alkyl or benzyl. 1. A method comprising: reacting dihydroxypyrrole of formula (2) with difluorobenzene of formula (3) to yield a compound of formula (4), and then saponifying and decarboxylating the compound of formula (4): A method for producing a compound according to claim 5. <Formula 2> <Formula 3> <Formula 4> Where R ¹ and R ² are each independently of each other H, C ₁ -C ₂₀ -alkyl, C ₆ -C ₁₀ -aryl, C ₇ -C ₁₂ -aralkyl, C ₁ -C ₁₈ -alkoxy, C ₂ -C ₁₈ -Hydroxyalkyleneoxy, C ₂ -C ₃₆ -alkoxyalkyleneoxy, hydroxyethyl, formyl, C ₂ -C ₁₈ -acyl, nitro, halogen, sulfo, cyano, carboxy, C ₁ -C _18- Alkoxycarbonyl or trifluoromethyl or together with the aromatic ring to which they are attached form an fused aromatic ring system, R ^{3 ′} represents C ₁ -C ₁₈ -alkoxycarbonyl, propylsulfonyl, butylsulfonyl, C ₁ -C ₂₀ -alkyl, C ₆ -C ₁₀ -aryl or C ₇ -C ₁₂ -aralkyl, R ^{4 ′} represents C ₁ -C ₁₈ -alkyl. Use of a compound according to any one of claims 1 to 5 for preparing an electrically conductive polymer. An electrically conductive polymer prepared by polymerizing a compound according to any one of claims 1 to 5. An electrically conductive polymer of the formula (5). <Formula 5> Where R ¹ and R ² are each independently of each other H, C ₁ -C ₂₀ -alkyl, C ₆ -C ₁₀ -aryl, C ₇ -C ₁₂ -aralkyl, C ₁ -C ₁₈ -alkoxy, C ₂ -C ₁₈ -Hydroxyalkyleneoxy, C ₂ -C ₃₆ -alkoxyalkyleneoxy, hydroxyethyl, formyl, C ₂ -C ₁₈ -acyl, nitro, halogen, sulfo, cyano, carboxy, C ₁ -C _18- Alkoxycarbonyl or trifluoromethyl or together with the aromatic ring to which they are attached form an fused aromatic ring system, R ^{3 ''} represents H, n represents the integer of 3-100. A compound of formula <Formula 4> Where R ¹ and R ² are each independently of each other H, C ₁ -C ₂₀ -alkyl, C ₆ -C ₁₀ -aryl, C ₇ -C ₁₂ -aralkyl, C ₁ -C ₁₈ -alkoxy, C ₂ -C ₁₈ -Hydroxyalkyleneoxy, C ₂ -C ₃₆ -alkoxyalkyleneoxy, hydroxyethyl, formyl, C ₂ -C ₁₈ -acyl, nitro, halogen, sulfo, cyano, carboxy, C ₁ -C _18- Alkoxycarbonyl or trifluoromethyl, or together with the aromatic ring to which they are attached, form a fused aromatic ring system, R ^{3 ′} represents C ₁ -C ₁₈ -alkoxycarbonyl, propylsulfonyl, butylsulfonyl, C ₁ -C ₂₀ -alkyl, C ₆ -C ₁₀ -aryl or C ₇ -C ₁₂ -aralkyl, R ^{4 ′} represents C ₁ -C ₁₈ -alkyl.