CN113666932A - Dimetatriazolopentacenequinone compound and preparation method thereof - Google Patents
Dimetatriazolopentacenequinone compound and preparation method thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 24
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 238000004440 column chromatography Methods 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- MVPKIPGHRNIOPT-UHFFFAOYSA-N 5,6-dimethyl-2h-benzotriazole Chemical compound C1=C(C)C(C)=CC2=NNN=C21 MVPKIPGHRNIOPT-UHFFFAOYSA-N 0.000 claims description 7
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 7
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical compound O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- YNRGDPQTVDWXPB-UHFFFAOYSA-N 3-(1,2,4-triazol-3-ylidene)-1,2,4-triazole Chemical compound N1=NC=NC1=C1N=NC=N1 YNRGDPQTVDWXPB-UHFFFAOYSA-N 0.000 claims 1
- 150000001347 alkyl bromides Chemical class 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 11
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- 230000003381 solubilizing effect Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000009825 accumulation Methods 0.000 abstract description 3
- 150000003852 triazoles Chemical class 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 16
- -1 bis-triazole pentacenequinone compound Chemical class 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 125000005997 bromomethyl group Chemical group 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- IGKLGCQYPZTEPK-UHFFFAOYSA-N pentacene-1,2-dione Chemical class C1=CC=C2C=C(C=C3C(C=C4C=CC(C(C4=C3)=O)=O)=C3)C3=CC2=C1 IGKLGCQYPZTEPK-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- DCZFGQYXRKMVFG-UHFFFAOYSA-N cyclohexane-1,4-dione Chemical compound O=C1CCC(=O)CC1 DCZFGQYXRKMVFG-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010129 solution processing Methods 0.000 description 2
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- 229920003026 Acene Polymers 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
Abstract
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:
Description
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.
Claims (10)
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.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070102696A1 (en) * | 2003-11-28 | 2007-05-10 | Beverley Brown | Organic semiconducting layers |
| US20080061287A1 (en) * | 2004-02-25 | 2008-03-13 | Kazuto Nagata | Polyacene Compound And Organic Semiconductor Thin Film |
| JP2010180140A (en) * | 2009-02-03 | 2010-08-19 | Japan Science & Technology Agency | Pentacenequinone derivative and method for producing the same |
| CN106883237A (en) * | 2017-04-05 | 2017-06-23 | 兰州大学 | A kind of pair of triazole pentacene quinones and preparation method thereof |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070102696A1 (en) * | 2003-11-28 | 2007-05-10 | Beverley Brown | Organic semiconducting layers |
| US20080061287A1 (en) * | 2004-02-25 | 2008-03-13 | Kazuto Nagata | Polyacene Compound And Organic Semiconductor Thin Film |
| JP2010180140A (en) * | 2009-02-03 | 2010-08-19 | Japan Science & Technology Agency | Pentacenequinone derivative and method for producing the same |
| CN106883237A (en) * | 2017-04-05 | 2017-06-23 | 兰州大学 | A kind of pair of triazole pentacene quinones and preparation method thereof |
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