阅读说明：本技术 一种双偏三唑并五苯醌化合物及其制备方法 (Dimetatriazolopentacenequinone compound and preparation method thereof ) 是由 师自法 满涛 许年胜 于 2020-05-14 设计创作，主要内容包括：本发明提供一种双偏三唑并五苯醌化合物,其化学命名为：1,9-二(R)-并五苯[2,3-d:9,10-d']二([1,2,3]三唑)-6,14(1H,9H)-二酮类化合物,其结构通式如下：其中R所代表的基团选自：己基、辛基、十二烷基,还提供式(Ⅰ)所示的化合物的制备方法。该化合物是一种N型有机半导体材料,助溶烷基链与共轭体系接近垂直,有助于形成J堆积,提高性能。(The invention provides a bimetatriazolopentabenzoquinone compound, which is chemically named as follows: 1, 9-di (R) -pentacene [2,3-d:9,10-d']Bis ([1,2, 3)]Triazole) -6,14(1H,9H) -diketone compounds have the following structural general formula:)

1. A bis-unsym-triazolopentaquinone compound, chemically designated as: 1, 9-di (R) -pentacene [2,3-d:9,10-d' ] bis ([1,2,3] triazole) -6,14(1H,9H) -diketone compound, which has the following structural general formula:

wherein R is: hexyl, octyl, dodecyl.

2. The method for preparing the 1, 9-di (R) -pentacene [2,3-d:9,10-d' ] bis ([1,2,3] triazole) -6,14(1H,9H) -dione compound of the bis-triazol pentaquinone compound according to claim 1 is characterized by comprising the following steps:

1) dissolving 5, 6-dimethyl-1H-benzo [ d ] [1,2,3] triazole, sodium hydroxide and tetrabutylammonium bromide in DMSO, and reacting with alkyl bromide under the protection of argon to synthesize a compound shown as a formula (II) shown as the following structural formula:

2) adding a compound shown in a formula (II), N-bromosuccinimide and benzoyl peroxide into carbon tetrachloride for reaction to synthesize a compound shown in a formula (III) shown in the following structural formula:

3) adding the compound of the formula (III) into acetonitrile, completely dissolving, and adding N-methylmorpholine oxide to synthesize the compound of the formula (IV) shown as the following structural formula:

4) adding the compound shown in the formula (IV) into absolute ethyl alcohol to dissolve the compound; adding ethanol solution of cyclohexanedione and potassium hydroxide into the reaction system until the color is just changed, and mixing, dissolving and recrystallizing by using methanol and dichloromethane to obtain the compound shown in the formula (I):

3. the process for producing 1, 9-bis (R) -pentacene [2,3-d:9,10-d' ] bis ([1,2,3] triazole) -6,14(1H,9H) -diones according to claim 2, wherein: the specific method of the step 1) is that 5, 6-dimethyl-1H-benzo [ d ] [1,2,3] triazole, sodium hydroxide and tetrabutylammonium bromide are dissolved in DMSO; removing air in the system, and filling argon into the system for protection; adding bromoalkane, stirring at room temperature for reaction for 1-18h, adding ethyl acetate for extraction, washing the organic phase with water for three times, washing with saturated saline solution, drying with anhydrous magnesium sulfate, concentrating, and purifying the product by column chromatography to obtain the compound shown in the formula (II).

4. The process for producing 1, 9-bis (R) -pentacene [2,3-d:9,10-d' ] bis ([1,2,3] triazole) -6,14(1H,9H) -dione compounds according to claim 2 or 3, characterized in that: the molar ratio of the 5, 6-dimethyl-1H-benzo [ d ] [1,2,3] triazole to the sodium hydroxide to the tetrabutylammonium bromide is 1:1.2: 0.1.

5. The process for producing 1, 9-bis (R) -pentacene [2,3-d:9,10-d' ] bis ([1,2,3] triazole) -6,14(1H,9H) -diones according to claim 2, wherein: step 2) the concrete method is that the compound shown in the formula (II), N-bromosuccinimide and benzoyl peroxide are added into carbon tetrachloride, and the mixture is refluxed for 2 to 14 hours; the reaction mixture was filtered with suction and the solvent was removed under reduced pressure to give the compound of formula (III).

6. The process for producing 1, 9-bis (R) -pentacene [2,3-d:9,10-d' ] bis ([1,2,3] triazole) -6,14(1H,9H) -diones according to claim 5, wherein: the molar ratio of the compound shown in the formula (II), the N-bromosuccinimide and the benzoyl peroxide is 1:2.4: 0.1.

7. The process for producing 1, 9-bis (R) -pentacene [2,3-d:9,10-d' ] bis ([1,2,3] triazole) -6,14(1H,9H) -diones according to claim 2, wherein: step 3) the concrete method is that the compound of the formula (III) is added into acetonitrile, and N-methylmorpholine oxide is added after the compound is completely dissolved; stirring and reacting for 2-24 hours at room temperature; removing the solvent under reduced pressure, washing with water, extracting with dichloromethane, washing the organic phase with saturated edible water, drying, concentrating, and purifying by column chromatography to obtain the compound of formula (IV).

8. The process for the preparation of 1, 9-bis (R) -pentacene [2,3-d:9,10-d' ] bis ([1,2,3] triazole) -6,14(1H,9H) -diones according to claim 7, characterized by: the molar ratio of the compound (III) and the N-methylmorpholine oxide is 1: 7.

9. The process for producing 1, 9-bis (R) -pentacene [2,3-d:9,10-d' ] bis ([1,2,3] triazole) -6,14(1H,9H) -diones according to claim 2, wherein: step 4) the specific method is that the compound of the formula (IV) is added into absolute ethyl alcohol to be dissolved; adding cyclohexanedione into the reaction system, stirring, heating to 20-70 ℃, then adding an ethanol solution (30%) of potassium hydroxide until the color is changed right, and stirring for 1-24 hours at 20-70 ℃; filtering out the solid, adding ethanol (5 times of the weight of the cyclohexanedione), carrying out ultrasonic treatment for 1-50 minutes, then carrying out suction filtration again, repeating the process for three times, and finally, mixing, dissolving and recrystallizing by using methanol and dichloromethane to obtain the compound shown in the formula (I).

10. The process for producing 1, 9-bis (R) -pentacene [2,3-d:9,10-d' ] bis ([1,2,3] triazole) -6,14(1H,9H) -diones according to claim 2, wherein: the molar ratio of the compound (IV) to the cyclohexanedione is 2: 1.

Technical Field

The invention belongs to the technical field of chemical synthesis, and particularly relates to a bis-triazole pentacenequinone compound and a preparation method thereof, wherein the chemical name of the compound is as follows: 1, 9-bis (R) -pentacene [2,3-d:9,10-d' ] bis ([1,2,3] triazole) -6,14(1H,9H) -dione.

Background

The substituted pentacenequinone LUMO has low orbital energy and has the properties of an N-type semiconductor. Most of the pentacene quinone compounds have poor solubility in solvents, which causes great inconvenience in device processing. The triazole with solubilizing groups at both ends of pentacenequinone can improve the solubility of the compound. When the solubilizing groups are connected at the 2-position and the 10-position, the triazolopentaquinone can be dissolved in an organic solvent, and the processing of devices is facilitated. But its semiconductor performance is low.

The invention provides a di-meta-triazolo-pentabenzoquinone compound and a preparation method thereof. The solubilizing groups are connected to the 1 position and the 9 position, and can be dissolved in an organic solvent to facilitate device processing. And the cosolvent alkyl chain is vertical to the acene conjugated system, which is beneficial to forming J accumulation and improving the mobility.

Disclosure of Invention

The invention provides a1, 9-di (R) -pentacene [2,3-d:9,10-d' ] di ([1,2,3] triazole) -6,14(1H,9H) -diketone compound aiming at poor solubility of pentacene quinone organic N-type semiconductor material in the prior art, and the compound is used for manufacturing a semiconductor device and can be dissolved in an organic solvent.

Another object of the present invention is to provide a process for the preparation of 1, 9-bis (R) -pentacene [2,3-d:9,10-d' ] bis ([1,2,3] triazole) -6,14(1H,9H) -diones.

The technical scheme is as follows for solving the technical problem of the invention:

1, 9-di (R) -pentacene [2,3-d:9,10-d' ] bis ([1,2,3] triazole) -6,14(1H,9H) -diketone compound, which has the following structural general formula:

wherein R is: hexyl, octyl, dodecyl.

The preparation method of the 1, 9-di (R) -pentacene [2,3-d:9,10-d' ] di ([1,2,3] triazole) -6,14(1H,9H) -diketone compound is as follows:

1) synthesizing a compound of formula (II) shown by the following structural formula:

dissolving 5, 6-dimethyl-1H-benzo [ d ] [1,2,3] triazole, sodium hydroxide and tetrabutylammonium bromide in DMSO; removing air in the system, and filling argon into the system for protection; adding bromoalkane, and stirring at room temperature for reaction; after reacting for 1-18 hours, adding ethyl acetate for extraction, washing the organic phase with water for three times, then washing with saturated saline, then drying with anhydrous magnesium sulfate, concentrating, and purifying the product by column chromatography to obtain the compound of formula (II).

2) Synthesizing a compound of formula (III) shown in the following structural formula:

adding a compound shown as a formula (II), N-bromosuccinimide and benzoyl peroxide into carbon tetrachloride, and refluxing the mixture for 2-14 hours; the reaction mixture was filtered with suction and the solvent was removed under reduced pressure to give the compound of formula (III).

3) Synthesizing a compound of formula (IV) shown by the following structural formula:

adding the compound shown in the formula (III) into acetonitrile, and adding N-methylmorpholine oxide after the compound is completely dissolved; stirring and reacting for 2-24 hours at room temperature; removing the solvent under reduced pressure, washing with water, extracting with dichloromethane, washing the organic phase with saturated edible water, drying, concentrating, and purifying by column chromatography to obtain the compound of formula (IV).

4) Synthesizing a compound of formula (V) represented by the following structural formula:

adding the compound shown in the formula (IV) into absolute ethyl alcohol to dissolve the compound; adding cyclohexanedione into the reaction system, stirring, heating to 20-70 ℃, adding an ethanol solution of potassium hydroxide at the temperature until the color is changed right, and stirring for 1-24 hours at 20-70 ℃; filtering out the solid, adding ethanol, performing ultrasonic treatment for 1-50 minutes, performing suction filtration again, repeating the process for three times, and finally, mixing, dissolving and recrystallizing by using methanol and dichloromethane to obtain the compound shown in the formula (I).

The compound of formula (I) provided by the invention is a pentacene quinone N-type organic semiconductor material. Because the alkyl has longer alkyl and good solubility, a solution processing method can be adopted in the preparation of the semiconductor device, and the preparation process is simplified. The solubilizing alkyl chain is vertical to the conjugated system, the steric hindrance of the aromatic ring in the long axis direction is reduced, J accumulation in the long axis direction is facilitated, and the device performance is improved.

Drawings

FIG. 1 is a flow chart of the preparation method of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

The application of the principles of the present invention will be further described with reference to the accompanying drawings and specific embodiments.

Example 1

1, 9-Dioctyl-pentacene [2,3-d:9,10-d' ] bis ([1,2,3] triazole) -6,14(1H,9H) -dione (A4)

The preparation of the compound of formula (A4) is as follows

S101: preparation of 5, 6-dimethyl-1-octyl-1H-benzo [ d ] [1,2,3] triazole (A1):

dissolve 5, 6-dimethyl-1H-benzo [ d ] [1,2,3] triazole (2.94g, 20mmol), sodium hydroxide (960mg, 24mmol), and a catalytic amount of tetrabutylammonium bromide in DMSO (250 mL); removing air in the reaction system and filling argon; adding 1-bromooctane (3.86g, 20mmol), and stirring at room temperature for reaction; after reacting for 16 hours, the mixture was extracted with ethyl acetate and washed with water, and the organic phase was washed with saturated brine, then dried (anhydrous magnesium sulfate), and concentrated. The product was purified by column chromatography (petrol ether/ethyl acetate, 15:1) to give the product (A1) (2.07g, 40%).

S102: preparation of 5, 6-bis (bromomethyl) -1-octyl-1H-benzo [ d ] [1,2,3] triazole (A2):

5, 6-dimethyl-1-octyl-1H-benzo [ d ] [1,2,3] triazole (A1) (0.81g, 3.14mmol), N-bromosuccinimide (1.29g, 7.22mmol) and benzoyl peroxide (75mg, 0.31mmol) were added to carbon tetrachloride (40mL) and stirred at 77 ℃ under reflux for 12 hours; the reaction mixture was filtered with suction and the solvent was removed under reduced pressure to give the crude product (A2).

S103: preparation of 1-octyl-1H-benzo [ d ] [1,2,3] triazole-5, 6-dialdehyde (A3):

the crude product 5, 6-bis (bromomethyl) -1-octyl-1H-benzo [ d ] [1,2,3] triazole (A2) (1.31g, 3.14mmol) was dissolved by adding to acetonitrile (100mL), and after the system was clear, N-methylmorpholine oxide (2.57g, 22mmol) was added; stirring the mixture for reaction at room temperature, and detecting the reaction degree by TLC; after completion of the reaction, the solvent was removed under reduced pressure, washed with water, extracted with dichloromethane, and the organic phase was washed with saturated brine, dried (anhydrous magnesium sulfate), and concentrated. The product was purified by column chromatography to give the product (A3) (478mg, 53% in total yield from S102 to S103).

S104: preparation of 1, 9-dioctylpentabenz [2,3-d:9,10-d' ] bis ([1,2,3] triazole) -6,14(1H,9H) -dione (A4):

1-octyl-1H-benzo [ d ] [1,2,3] triazole-5, 6-dialdehyde (A3) (0.95g, 3.3mmol) was added to an appropriate amount of anhydrous ethanol until just dissolved, 1, 4-cyclohexanedione (190mg, 1.7mmol) was added, stirred, and heated to 60 deg.C; an ethanolic solution of freshly prepared potassium hydroxide was added dropwise until the reaction mixture just discoloured and the reaction was carried out at this temperature for 1 hour. The solid was filtered off, a small amount of ethanol was added, sonicated for 10 minutes, then filtered again, and the process was repeated three times. The product (A4) was obtained (1.01g, 50%).

Example 2

1, 9-dihexyl-pentacene [2,3-d:9,10-d' ] bis ([1,2,3] triazole) -6,14(1H,9H) -dione (B4)

The preparation of the compound of the formula (B4) is as follows

S201: preparation of 5, 6-dimethyl-1-hexyl-1H-benzo [ d ] [1,2,3] triazole (B1):

dissolve 5, 6-dimethyl-1H-benzo [ d ] [1,2,3] triazole (2.94g, 20mmol), sodium hydroxide (960mg, 24mmol), and a catalytic amount of tetrabutylammonium bromide in DMSO (250 mL); removing air in the reaction system and filling argon; 1-bromohexane (3.30g,20mmol) was added and the reaction was stirred at room temperature; after reacting for 16 hours, the mixture was extracted with ethyl acetate and washed with water, and the organic phase was washed with saturated brine, then dried (anhydrous magnesium sulfate), and concentrated. The product was purified by column chromatography (petrol ether/ethyl acetate, 15:1) to give the product (B1) (1.94g, 42%).

S202: preparation of 5, 6-bis (bromomethyl) -1-hexyl-1H-benzo [ d ] [1,2,3] triazole (B2):

5, 6-dimethyl-1-hexyl-1H-benzo [ d ] [1,2,3] triazole (B1) (725mg, 3.14mmol), N-bromosuccinimide (1.29g, 7.22mmol) and benzoyl peroxide (75mg, 0.31mmol) were added to carbon tetrachloride (40mL), and stirred at 77 ℃ under reflux for 12 hours; the reaction mixture was filtered with suction and the solvent was removed under reduced pressure to give the crude product (B2).

S203: preparation of 1-hexyl-1H-benzo [ d ] [1,2,3] triazole-5, 6-dialdehyde (B3):

the crude product 5, 6-bis (bromomethyl) -1-hexyl-1H-benzo [ d ] [1,2,3] triazole (B2) (1.22g, 3.14mmol) was dissolved by adding to acetonitrile (100mL), and after the system was clear, N-methylmorpholine oxide (2.57g, 22mmol) was added; stirring the mixture for reaction at room temperature, and detecting the reaction degree by TLC; after completion of the reaction, the solvent was removed under reduced pressure, washed with water, extracted with dichloromethane, and the organic phase was washed with saturated brine, dried (anhydrous magnesium sulfate), and concentrated. The product was purified by column chromatography to give the product (B3) (407mg, 50% total yield from S202 to S203).

S204: preparation of 1, 9-dihexyl-pentacene [2,3-d:9,10-d' ] bis ([1,2,3] triazole) -6,14(1H,9H) -dione (B4):

adding 1-hexyl-1H-benzo [ d ] [1,2,3] triazole-5, 6-dialdehyde (B3) (855mg, 3.3mmol) into an appropriate amount of anhydrous ethanol until just dissolved, adding 1, 4-cyclohexanedione (190mg, 1.7mmol), stirring, and heating to 60 ℃; an ethanolic solution of freshly prepared potassium hydroxide was added dropwise until the reaction mixture just discoloured and the reaction was carried out at this temperature for 1 hour. The solid was filtered off, a small amount of ethanol was added, sonicated for 10 minutes, then filtered again, and the process was repeated three times. The product (B4) (1.01g, 55%) was obtained.

Example 3

1, 9-Didodecyl-pentacene [2,3-d:9,10-d' ] bis ([1,2,3] triazole) -6,14(1H,9H) -dione (C4)

The preparation of the compound of formula (C4) is as follows

S301: preparation of 5, 6-dimethyl-1-dodecyl-1H-benzo [ d ] [1,2,3] triazole (C1):

dissolve 5, 6-dimethyl-1H-benzo [ d ] [1,2,3] triazole (2.94g, 20mmol), sodium hydroxide (960mg, 24mmol), and a catalytic amount of tetrabutylammonium bromide in DMSO (250 mL); removing air in the reaction system and filling argon; adding 1-bromododecane (4.98g,20mmol), and stirring at room temperature for reaction; after reacting for 16 hours, the mixture was extracted with ethyl acetate and washed with water, and the organic phase was washed with saturated brine, then dried (anhydrous magnesium sulfate), and concentrated. The product was purified by column chromatography (petrol ether/ethyl acetate, 15:1) to give the product (C1) (2.71g, 43%).

S302: preparation of 5, 6-bis (bromomethyl) -1-dodecyl-1H-benzo [ d ] [1,2,3] triazole (C2):

5, 6-dimethyl-1- (dodecyl) -1H-benzo [ d ] [1,2,3] triazole (C1) (989mg, 3.14mmol), N-bromosuccinimide (1.29g, 7.22mmol) and benzoyl peroxide (75mg, 0.31mmol) were added to carbon tetrachloride (40mL) and stirred at 77 ℃ under reflux for 12 hours; the reaction mixture was filtered with suction and the solvent was removed under reduced pressure to give the crude product (C2).

S303: preparation of 1-dodecyl-1H-benzo [ d ] [1,2,3] triazole-5, 6-dialdehyde (C3):

the crude product 5, 6-bis (bromomethyl) -1-dodecyl-1H-benzo [ d ] [1,2,3] triazole (C2) (1.49g, 3.14mmol) was dissolved by adding to acetonitrile (100mL), and after the system was clear, N-methylmorpholine oxide (2.57g, 22mmol) was added; stirring the mixture for reaction at room temperature, and detecting the reaction degree by TLC; after completion of the reaction, the solvent was removed under reduced pressure, washed with water, extracted with dichloromethane, and the organic phase was washed with saturated brine, dried (anhydrous magnesium sulfate), and concentrated. The product was purified by column chromatography to give the product (C3) (539mg, 50% total yield from S402 to S403).

S304: preparation of 1, 9-di (dodecyl) -pentacene [2,3-d:9,10-d' ] bis ([1,2,3] triazole) -6,14(1H,9H) -dione (C4):

1-dodecyl-1H-benzo [ d ] [1,2,3] triazole-5, 6-dialdehyde (C3) (1.13g, 3.3mmol) was added to an appropriate amount of anhydrous ethanol until just dissolved, 1, 4-cyclohexanedione (190mg, 1.7mmol) was added, stirred, and heated to 60 deg.C; an ethanolic solution of freshly prepared potassium hydroxide was added dropwise until the reaction mixture just discoloured and the reaction was carried out at this temperature for 1 hour. The solid was filtered off, a small amount of ethanol was added, sonicated for 10 minutes, then filtered again, and the process was repeated three times. The product (C4) (1.20g, 50%) was obtained.

The working principle of the invention is as follows: the present invention provides a method for producing 1, 9-dioctyl-pentacene [2,3-d:9,10-d ] bis ([1,2,3] triazole) -6,14(1H,9H) -dione, 1, 9-dihexyl-pentacene [2,3-d:9,10-d '] bis ([1,2,3] triazole) -6,14(1H,9H) -dione, 1, 9-didodecyl) -pentacene [2,3-d:9,10-d' ] bis ([1, the N-type organic semiconductor material which has excellent performances such as 2,3] triazole) -6,14(1H,9H) -diketone and the like and can be dissolved in an organic solvent and the synthesis method thereof can be prepared into a semiconductor device by a solution processing method, overcome the defect of extremely poor solubility of the traditional substituted pentacene quinone compound, provide convenience for preparing the N-type semiconductor device, and form J aggregation in a solid to improve the performance of the semiconductor.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.