Naphthodioxazine imide compounds and methods of preparation

Abstract

This paper discloses a class of naphthodioxazine imide compounds and their preparation method, belonging to the field of organic materials. These naphthodioxazine imide compounds are derived from traditional triphenyldioxazines. First, a naphthodioxazine intermediate is synthesized using xylene as a raw material to increase the benzene ring structure of the triphenyldioxazine, thus expanding its conjugated structure. It is the first time that two naphtho rings have been introduced to replace the benzene ring in the triphenyldioxazine imide. By introducing long amine chains and other substituents onto the imide, this compound exhibits high solubility in common organic solvents. By expanding the conjugated area and increasing the electron cloud distribution, the compound exhibits strong absorption in the visible light region and a high molar extinction coefficient. It also possesses good redox properties and electron transport performance, making it suitable for application as an optoelectronic material in the field of organic optoelectronics.

Description

Technical Field

[0001] This invention relates to a class of naphthodioxazine imide compounds and their preparation methods, which belong to the field of organic synthesis. Background Technology

[0002] The entire molecule of triphenyldioxazine imide consists of a central triphenyldioxazine backbone and two bicarboxylic acid imides. Its advantages include strong absorption in the visible light region, a high molar extinction coefficient, fluorescence quantum yield, good photostability, and thermal stability, making it a high-performance organic semiconductor material. By improving the structure of triphenyldioxazine imide and increasing conjugation, organic semiconductor materials with even better performance can be obtained.

[0003] In 2017, our research group designed and synthesized a conjugated bridged diploid structure of triphenyldioxazinimide. In 2020, we synthesized a diploid triphenyldioxazinimide with direct C / C single bond linkage and studied its properties. In 2022, our group designed and synthesized triphenyldioxazine compounds and their homocoordinate complexes. However, we have not yet directly improved the conjugated structure of the triphenyldioxazine parent compound itself. Designing and synthesizing naphthodioxazinimide compounds is a challenging task, and the optical properties of these naphthodioxazinimide compounds deserve further investigation. To date, no compounds involving naphthodioxazinimides have been found. Summary of the Invention

[0004] To address the problems existing in the prior art, this invention provides a class of naphthodioxazine imide compounds and a method for their preparation. By increasing the number of benzene rings to expand the conjugated structure of the triphenyldioxazine parent compound, a new class of N-type semiconductor materials with excellent photoelectric properties is obtained.

[0005] To achieve the purpose of the invention, the present invention adopts the following technical solution: a class of naphthodioxazine imide compounds having the following general structural formula:

[0006]

[0007] Wherein: R1 and R2 are each independently selected from hydrogen atoms, groups containing substituents or not containing substituents, and the groups containing substituents or not containing substituents are selected from C1-C30 alkyl, C1-C30 fluoroalkyl, C3-C30 cycloalkyl, C3-C30 fluorocycloalkyl, C5-C30 aryl, C5-C30 fluoroaryl, C1-C30 heterocyclic, C1-C30 fluoroheterocyclic, C6-C30 alkylaryl, C3-C30 alkylheterocyclic, C1-C30 alkoxy, C1-C30 fluoroalkoxy, and C2-C30 alkoxyalkyl.

[0008] In some specific compounds, the substituent or non-substituent group is a C1-C20 alkyl group, a C1-C20 fluoroalkyl group, a C1-C20 alkoxy group, a C1-C20 fluoroalkoxy group, a C4-C20 cycloalkyl group, a C4-C20 fluorocycloalkyl group, a C5-C20 aryl group, a C5-C20 fluoroaryl group, a C1-C20 heterocyclic group, or a C1-C20 fluoroheterocyclic group.

[0009] In some specific compounds, the substituent-containing or non-substituent group is perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluoron-butyl, perfluorosec-butyl, perfluoroisobutyl, perfluorotert-butyl, especially perfluorobutyl, perfluorodecyl, perfluorododecylethyl, 1H-perfluoroundecyl, 1H-perfluorododecyl, 1,1,1,2,2,3,3,4,4-nonafluorododecyl, 1,1,2 2,3,3,4,4,5,5,6,6-Tridecylfluoro-9-heptoxy-nonylalkyl, fluorocyclohexylalkyl, 1-ethyl-4-fluorophenyl, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecylalkyl, dodecylalkyl, tridecylalkyl, tetradecylalkyl, pentadecylalkyl, hexadecylalkyl, heptadecanylalkyl, octadecylalkyl, nonadecanylalkyl, eicosylalkyl, methyl Oxygen, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecylalkoxy, dodecylalkoxy, tridecylalkoxy, tetradecylalkoxy, pentadecylalkoxy, hexadecylalkoxy, heptadecanylalkoxy, octadecylalkoxy, nonadecanylalkoxy, eicosylalkoxy, phenyl, naphthyl, anthraceneyl, phenanthrene, tetraphenyl, pentaphenyl, hexaphenyl, pyrene Indene, biphenyl, fluorenyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, undecylcycloalkyl, dodecylcycloalkyl, tridecylcycloalkyl, tetradecylcycloalkyl, pentadecylcycloalkyl, hexadecylcycloalkyl, heptadecanylcycloalkyl, octadecylcycloalkyl, nonadecylcycloalkyl, eicosylcycloalkyl, thiophene, pyrrole, furanyl, pyridyl, groups derived from the fusion of the ring of the above heteroaryl groups with the ring of the aryl group described above, or combinations of the above heteroaryl groups. These groups constituting heteroaryl groups may contain additional substituents.

[0010] The substituents are selected from the following groups: alkyl, preferably alkyl having 1-16 carbon atoms; alkoxy, preferably alkoxy having 1-16 carbon atoms; aryl, preferably aryl having 5-16 carbon atoms; cycloalkyl, preferably cycloalkyl having 3-16 carbon atoms; heterocyclic group, preferably heterocyclic group having 5-16 carbon atoms, wherein the heteroatom included in the heterocyclic group is selected from B, Si, O, Sn, N, S, P, Se; heteroaryl, particularly heteroaryl having 1-16 carbon atoms; heteroarylalkyl, particularly composed of an aryl having 5-16 carbon atoms and an alkyl part having 1-16 carbon atoms. The following groups are included in the composition of heteroaryl groups; heteroarylalkoxy groups, preferably heteroarylalkoxy groups composed of aryl groups having 5-16 carbon atoms and alkoxy groups having 1-16 carbon atoms; alkenyl groups, especially allyl, 2-butenyl, 3-pentenyl, etc.; alkynyl groups, especially propynyl, 3-pentynyl, etc.; amino substituents, especially amino, imino and methylamino, dimethylamino, etc.; acyl groups, preferably formyl, acetyl, benzoyl, etc.; alkylthio groups, preferably methylthio, ethylthio, etc.; heteroarylthio groups, especially pyridylthio, etc.; heterocyclic groups, preferably imidazolyl, pyridinyl, etc.; hydroxyl groups; halogen atoms; cyano groups; aldehyde groups; ester groups; nitro groups.

[0011] In some specific compounds, the substituents are selected from C1-C16 alkyl, C1-C16 fluoroalkyl, C1-C16 alkoxy, C5-C16 aryl, C3-C16 cycloalkyl, C1-C16 heterocyclic, C1-C5 acyl, hydroxyl, halogen, and nitro groups.

[0012] In some specific compounds, the substituent is at least one selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, hydroxyl, mercapto, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano, aldehyde, ester, sulfonic acid group, sulfinic acid group, nitro, amino, imino, carboxyl, and hydrazine.

[0013] In some specific compounds, the substituent or non-substituent groups are C1-C30 perfluoroalkyl or C1-C30 semifluorinated alkyl groups.

[0014] The preparation method of the aforementioned naphthodioxazine imide compound is as follows: Compound A is mixed with dihydroxybenzoquinone, and the mixture is stirred and heated to react, thereby obtaining the aforementioned naphthodioxazine imide compound, as shown in the following formula:

[0015]

[0016] The definitions of R1 and R2 are the same as those in the general structural formula.

[0017] The heating temperature of the preparation method is 90-120℃, the reaction time is 8-12 hours, and the amount of compound A is 2.1-2.5 times the amount of dihydroxybenzoquinone. The preparation method is carried out in an organic solvent, which is one or more of chloroform and glacial acetic acid.

[0018] Synthesis of compound naphthoimide A:

[0019]

[0020] The definition of R is the same as the definition in the structure.

[0021] Preparation method: Liquid bromine was added dropwise to o-xylene and iodine granules in a dichlorosolvent under an ice-salt bath. After complete addition, the reaction was allowed to proceed for 24 hours to obtain the brominated product. The product was dissolved in chloroform and NBS and AIBN were added. The reaction was carried out under iodine-tungsten lamp irradiation for 8 hours. The resulting product was reacted with dimethyl fumarate and KI in DMF solution at 80°C for 8 hours. In the next step, the product was stirred in a methanol and water solvent containing potassium hydroxide, followed by the addition of dilute hydrochloric acid and stirring for 30 minutes. The resulting product was distilled under reduced pressure at 230°C to obtain a naphthoic anhydride product. This product was reacted with R-NH3 in a pyridine solvent at 120°C for 8 hours, followed by the reaction with sodium nitrite in DMF solvent at 120°C for 12 hours. After treatment with dilute hydrochloric acid, palladium on carbon was hydrogenated to obtain compound A.

[0022] The aforementioned triphenyldioxazine imide diploid derivative is used as a photoelectric material in the fields of solar cells, light-emitting diodes, organic thermoelectric devices, and organic field-effect transistors.

[0023] The beneficial effects of this invention are as follows: The naphthodioxazinimide compounds provided by this invention innovatively replace the benzene rings with two naphthalene rings in triphenyldioxazinimides. Due to the increased conjugated area, the electrochemical and spectroscopic properties of the triphenyldioxazinimide molecule are improved, and the introduction of long amine chains on the dovetail grooves results in superior solubility. This compound exhibits high solubility in common organic solvents, readily soluble in dichloromethane, chloroform, toluene, chlorobenzene, etc., with a solubility in dichloromethane exceeding 60 mg / mL. Compared to other methods for preparing triphenyldioxazinimide derivatives, this preparation method is simple and efficient, requiring only heating with glacial acetic acid without any additional conditions, making the reaction conditions simpler and the cost lower. This derivative exhibits a very strong absorption peak and a high molar extinction coefficient in the 300-650 nm visible light region, reaching as high as 3 × 10⁻⁶. 5 M -1 cm -1The light-harvesting properties of this compound are significantly higher than those of other existing triphenyldioxazine imide derivatives. Furthermore, the compound exhibits excellent light-harvesting performance, demonstrating its advantages as an organic optoelectronic material. It also possesses very good redox properties and high electron-accepting ability; its LUMO energy level, determined and calculated using cyclic voltammetry, ranges from -3.9 eV to -5.0 eV. Based on these superior optoelectronic properties, this type of derivative shows great promise for applications in solar cells, organic light-emitting diodes, and organic field-effect transistors. Attached Figure Description

[0024] Figure 1 This is the ultraviolet absorption spectrum of compound B3.

[0025] Figure 2 These are the cyclic voltammetry curves for compound B3. Detailed Implementation

[0026] To make the technical solutions of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The following embodiments are used to illustrate the present invention, but are not intended to limit the scope of the present invention.

[0027] Example A1

[0028]

[0029] 1 g of the brominated xylene product, 16 g of NBS, and 0.1 g of AIBN were reacted in 20 ml of chlorobenzene solvent under iodine-tungsten lamp irradiation for 8 h. After the reaction was complete, the product was extracted with dichloromethane, washed three times with water, and the dichloromethane was evaporated under reduced pressure. Column chromatography yielded 2.2 g of product 1 (80% yield, HRMS: found 520.7208). 11 g of product 1 was reacted with 0.24 g of dimethyl fumarate and 1.14 g of KI in 20 ml of DMF solution at 120 °C for 10 h. After the reaction was complete, the product was extracted with dichloromethane, washed three times with water, and the dichloromethane was evaporated under reduced pressure. Column chromatography yielded 0.44 g of product 3 (76% yield, HRMS: found 301.2100). Product 3 was stirred in a solution of potassium hydroxide in methanol and water for 30 h, then dilute hydrochloric acid was added and stirred for 1 h, extracted with dichloromethane, washed with water, and the dichloromethane was evaporated under reduced pressure to obtain product 4, with a yield of 70% and HRMS: found 321.4100. Product 4 was distilled under reduced pressure at 230 °C to obtain product 5 (HRMS: found 353.5860). 1 g of product 5 was reacted with 0.7 g of an amine chain in 10 mL of pyridine solvent at 120 °C for 8 h. After the reaction was complete, the product was treated with dilute hydrochloric acid, extracted with dichloromethane, washed three times with water, and the dichloromethane was evaporated under reduced pressure. Column chromatography yielded 0.82 g of product c1 (60% yield, HRMS: found 412.1008). 1 g of product c1 was reacted with 0.52 g of sodium nitrite in DMF solution at 120 °C for 12 h. After treatment with dilute hydrochloric acid, the product was extracted with dichloromethane, washed three times with water, and the dichloromethane was evaporated under reduced pressure. Column chromatography yielded 0.75 g of product b1 (95% yield, HRMS: found 398.1763). 0.2 g of palladium on carbon was added to product b11 g, followed by 10 ml of tetrahydrofuran solvent. The mixture was then purged with hydrogen gas to 3 MPa and reacted at 90 °C for 7 h. The solvent was removed by vacuum drying to obtain compound A1 0.79 g. HRMS: found 382.2165.

[0030] Example A2

[0031]

[0032] The method for synthesizing product 5 was the same as in Example A1. 1 g of product 5 was reacted with 0.8 g of the amine chain in 10 ml of pyridine solvent at 120 °C for 8 h. After the reaction was complete, the product was treated with dilute hydrochloric acid, extracted with dichloromethane, washed three times with water, and the dichloromethane was evaporated under reduced pressure. The product was then subjected to column chromatography followed by nitration with sodium nitrite, treatment with hydrochloric acid, and separation by column chromatography to obtain 0.89 g of product b2 (65% yield, HRMS: found 440.2308). 1 g of product b2 and 0.1 g of palladium on carbon were added to 10 ml of tetrahydrofuran solvent, purged with hydrogen to 3 MPa, and reacted at 90 °C for 7 h. The solvent was removed by vacuum evaporation to obtain 0.83 g of compound A2 (HRMS: found 410.5678).

[0033] Example A3

[0034]

[0035] The synthesis method of compound A3 is as described in Example A2.

[0036] Example A4

[0037]

[0038] The synthesis method of compound A4 is as described in Example A2.

[0039] Example A9

[0040]

[0041] The synthesis method of compound A9 is as described in Example A2.

[0042] Example A10

[0043]

[0044] The synthesis method of compound A10 is as described in Example A2.

[0045] Example A12

[0046]

[0047] The synthesis method of compound A12 is as described in Example A2.

[0048] Example A16

[0049]

[0050] The synthesis method of compound A16 is as described in Example A2.

[0051] Example A19

[0052]

[0053] The synthesis method of compound A19 is as described in Example A2.

[0054] Example A23

[0055]

[0056] The synthesis method of compound A23 is as described in Example A2.

[0057] Example A25

[0058]

[0059] The synthesis method of compound A25 is as described in Example A2.

[0060] Example A26

[0061]

[0062] The synthesis method of compound A26 is as described in Example A2.

[0063] Example A28

[0064]

[0065] The synthesis method of compound A28 is as described in Example A2.

[0066] The synthesis methods of compounds A3-A28 are all the same as in Example A2.

[0067] Example 1

[0068]

[0069] Weigh 1 g of naphthoimide and 0.18 g of p-hydroxybenzoquinone into a reaction flask, add 25 ml of glacial acetic acid, and stir at 100 °C for 8 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.45 g of product, yield 42%, HRMS: found 832.4200.

[0070] Example 2

[0071]

[0072] Weigh 1 g of naphthoimide and 0.16 g of p-hydroxybenzoquinone into a reaction flask, add 25 ml of glacial acetic acid, and stir at 100 °C for 8 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.4 g of product, yield 40%, HRMS: found 888.4826.

[0073] Example 3

[0074]

[0075] Weigh 1 g of naphthoimide and 0.12 g of p-hydroxybenzoquinone into a reaction flask, add 25 ml of glacial acetic acid, and stir under reflux at 90 °C for 8 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.4 g of product, yield 40%, HRMS: found 1184.3207.

[0076] Example 4

[0077]

[0078] The synthesis method is the same as in Example 3.

[0079] Example 5

[0080]

[0081] Weigh 1 g of naphthoimide and 0.09 g of p-hydroxybenzoquinone into a reaction flask, add 5 ml of chloroform and 15 ml of glacial acetic acid, and stir under reflux at 90 °C for 8 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.35 g of product, yield 32%, HRMS: found 1470.0056.

[0082] Example 6

[0083]

[0084] Weigh 1 g of naphthoimide and 0.21 g of p-hydroxybenzoquinone into a reaction flask, add 5 ml of chloroform and 15 ml of glacial acetic acid, and stir under reflux at 90 °C for 8 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.29 g of product, yield 28%, HRMS: found 691.8991.

[0085] Example 7

[0086]

[0087] Weigh 1 g of naphthoimide and 0.14 g of p-hydroxybenzoquinone into a reaction flask, add 5 ml of chloroform and 15 ml of glacial acetic acid, and stir under reflux at 95 °C for 8 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.4 g of product, yield 40%, HRMS: found 984.1035.

[0088] Example 8

[0089]

[0090] Weigh 1 g of naphthoimide and 0.22 g of p-hydroxybenzoquinone into a reaction flask, add 10 ml of toluene and 15 ml of glacial acetic acid, and stir under reflux at 120 °C for 8 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.47 g of product, yield 43%, HRMS: found 675.9987.

[0091] Example 9

[0092]

[0093] The synthesis method is as described in Example 8.

[0094] Example 10

[0095]

[0096] Weigh 1 g of naphthoimide and 0.19 g of p-hydroxybenzoquinone into a reaction flask, add 10 ml of chlorobenzene and 15 ml of glacial acetic acid, and stir under reflux at 120 °C for 8 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.31 g of product, yield 28%, HRMS: found 766.7380.

[0097] Example 11

[0098]

[0099] Weigh 1 g of naphthoimide and 0.18 g of p-hydroxybenzoquinone into a reaction flask, add 10 ml of toluene and 15 ml of glacial acetic acid, and stir under reflux at 110 °C for 8 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.34 g of product, yield 34%, HRMS: found 787.9978.

[0100] Example 12

[0101]

[0102] Weigh 1 g of naphthoimide and 0.19 g of p-hydroxybenzoquinone into a reaction flask, add 10 ml of toluene and 15 ml of glacial acetic acid, and stir under reflux at 120 °C for 8 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.31 g of product, yield 30%, HRMS: found 753.0007.

[0103] Example 13

[0104]

[0105] Weigh 1 g of naphthoimide and 0.19 g of p-hydroxybenzoquinone into a reaction flask, add 15 ml of toluene and 10 ml of glacial acetic acid, and stir under reflux at 110 °C for 8 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.48 g of product, yield 44%, HRMS: found 756.1609.

[0106] Example 14

[0107]

[0108] Weigh 1 g of naphthoimide and 0.19 g of p-hydroxybenzoquinone into a reaction flask, add 15 ml of chlorobenzene and 10 ml of glacial acetic acid, and stir under reflux at 130 °C for 8 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.29 g of product, yield 28%, HRMS: found 776.1576.

[0109] Example 15

[0110]

[0111] Weigh 1 g of naphthoimide and 0.19 g of p-hydroxybenzoquinone into a reaction flask, add 15 ml of chlorobenzene and 10 ml of glacial acetic acid, and stir under reflux at 100 °C for 8 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.47 g of product, yield 37%, HRMS: found 740.1002.

[0112] Example 16

[0113]

[0114] Weigh 1 g of naphthoimide, 0.22 g of p-hydroxybenzoquinone, and 0.1 g of sulfurous acid into a reaction flask. Add 20 ml of toluene and 5 ml of glacial acetic acid. Stir and reflux at 120 °C for 10 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate to dryness under reduced pressure, and separate by column chromatography to obtain 0.3 g of product, yield 28%, HRMS: found 687.8759.

[0115] Example 17

[0116]

[0117] Weigh 1 g of naphthoimide and 0.22 g of p-hydroxybenzoquinone into a reaction flask, add 25 ml of DMF, and stir under reflux at 140 °C for 12 hours. After the reaction is complete, evaporate the reaction solution to dryness under reduced pressure, and separate by column chromatography to obtain 0.25 g of product, yield 23%, HRMS: found 679.1002.

[0118] Example 18

[0119]

[0120] Weigh 1 g of naphthoimide and 0.126 g of p-hydroxybenzoquinone into a reaction flask, add 10 ml of dichlorobenzene and 15 ml of glacial acetic acid, and stir under reflux at 95 °C for 8 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.57 g of product, yield 54%, HRMS: found 1124.6754.

[0121] Example 19

[0122]

[0123] Weigh 1 g of naphthoimide and 0.18 g of p-hydroxybenzoquinone into a reaction flask, add 25 ml of glacial acetic acid, and stir under reflux at 90 °C for 10 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.43 g of product, yield 40%, HRMS: found 802.3067.

[0124] Example 20

[0125]

[0126] Weigh 1 g of naphthoimide and 0.2 g of p-hydroxybenzoquinone into a reaction flask, add 15 ml of chloroform and 10 ml of glacial acetic acid, and stir under reflux at 85 °C for 8 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.49 g of product, yield 39%, HRMS: found 862.3678.

[0127] Example 21

[0128]

[0129] Weigh 1 g of naphthoimide and 0.09 g of p-hydroxybenzoquinone into a reaction flask, add 15 ml of acetone and 10 ml of glacial acetic acid, and stir under reflux at 95 °C for 6 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.3 g of product, yield 24%, HRMS: found 1624.3671.

[0130] Example 22

[0131]

[0132] Weigh 1 g of naphthoimide and 0.12 g of p-hydroxybenzoquinone into a reaction flask, add 10 ml of dioxane and 15 ml of glacial acetic acid, and stir under reflux at 110 °C for 6 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.34 g of product, yield 35%, HRMS: found 1212.1003.

[0133] Example 23

[0134]

[0135] Weigh 1 g of naphthoimide and 0.12 g of p-hydroxybenzoquinone into a reaction flask, add 10 ml of dioxane and 15 ml of glacial acetic acid, and stir under reflux at 80 °C for 6 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.24 g of product, yield 23%, HRMS: found 1212.4739.

[0136] Example 24

[0137]

[0138] Weigh 1 g of naphthoimide and 0.14 g of p-hydroxybenzoquinone into a reaction flask, add 10 ml of chlorobenzene and 10 ml of glacial acetic acid, and stir under reflux at 95 °C for 8 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.4 g of product, yield 38%, HRMS: found 1030.1739.

[0139] Example 25

[0140]

[0141] Weigh 1 g of naphthoimide and 0.08 g of p-hydroxybenzoquinone into a reaction flask, add 10 ml of dioxane and 10 ml of glacial acetic acid, and stir under reflux at 85 °C for 7 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.21 g of product, yield 19%, HRMS: found 1816.9763.

[0142] Example 26

[0143]

[0144] Weigh 1 g of naphthoimide and 0.16 g of p-hydroxybenzoquinone into a reaction flask, add 10 ml of dioxane and 15 ml of glacial acetic acid, and stir under reflux at 100 °C for 5 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.25 g of product, yield 24%, HRMS: found 880.2013.

[0145] Example 27

[0146]

[0147] Weigh 1 g of naphthoimide and 0.2 g of p-hydroxybenzoquinone into a reaction flask, add 10 ml of dioxane and 15 ml of glacial acetic acid, and stir under reflux at 95 °C for 6 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.23 g of product, yield 23%, HRMS: found 720.0058.

[0148] Example 28

[0149]

[0150] Weigh 1 g of naphthoimide and 0.14 g of p-hydroxybenzoquinone into a reaction flask, add 10-chlorobenzene and 15 ml of glacial acetic acid, and stir under reflux at 110 °C for 8 hours. After the reaction is complete, extract with dichloromethane, wash three times with water, evaporate dichloromethane under reduced pressure, and separate by column chromatography to obtain 0.18 g of product, yield 18%, HRMS: found 1016.9325.

[0151] Example 29

[0152] The properties of the semi-perfluorododecylamine naphthodioxazine imide (compound B3) obtained in Example 3 were studied.

[0153] The UV-Vis spectrum of semi-perfluorododecylaminenaphthodioxazineimide was measured using an HP8543 UV spectrophotometer (USA). Compound B3 was first prepared at a concentration of 1.0 × 10⁻⁶. -3 The stock solution was diluted to 1.0 × 10⁻⁶ mol / L with dichloromethane solution. -6 mol / L, and its UV-Vis absorption spectrum was measured. For example... Figure 1 As shown, this material exhibits very strong absorption in the 300-600 nm visible light region, with a maximum absorption peak at 539 nm. The molar extinction coefficient of this material is calculated using the formula A = abc, and it is 382000 MΩ. -1 cm -1 (In the formula, A is absorbance, b is the thickness of the sample cell, and c is the molar concentration.) Its molar extinction coefficient is twice that of triphenyldioxazine imide at the same concentration; according to the formula... Find the optical band gap E ｇ The value is 2.03 eV, demonstrating the material's excellent light-harvesting properties. Furthermore, the presence of some distortion between the large conjugated planes helps suppress intermolecular aggregation, and its solubility in dichloromethane is greater than 60 mg / mL, indicating good solubility.

[0154] Example 30

[0155] Cyclic voltammetry was performed on the semi-perfluorododecylamine naphthodioxazinimide compound obtained in Example 3 using a BSA100B / W electrochemical analysis system. A three-electrode system was employed, with a glassy carbon electrode as the working electrode, a saturated calomel electrode as the reference electrode, and a platinum wire electrode as the control electrode. Compound B3 was accurately weighed and prepared into a 10 mg / ml dichloromethane solution, and tetrabutylammonium hexafluorophosphate was added as the electrolyte. The cyclic voltammetry curve was obtained as shown below. Figure 2 As shown, this compound exhibits two sets of reversible redox peaks. It can accept two electrons, demonstrating a stronger electron-accepting ability compared to other derivatives. The onset potential of the first reduction peak was determined to be -0.532 eV from the cyclic voltammetry curve. Using ferrocene as an internal standard couple, and referring to the literature, the absolute value of the ferrocene couple relative to vacuum is 4.8 eV. Based on the formula... Its LUMO energy level was calculated to be -4.27 eV. Then, according to the formula E... HOMO =(E LUMO -E g The HOMO energy level was calculated to be -6.30 eV, demonstrating that the material possesses excellent redox properties.

[0156] Example 31

[0157] The spectroscopic properties, electrochemical properties, and solubility data of compounds B2, B13, B15, B18, B21, B22, and B28 are given in the following table. The spectroscopic properties were tested using the same method as in Example 29, and the electrochemical properties were tested using the same method as in Example 30.

[0158] Table 1. Spectroscopic properties, electrochemical properties, and solubility data of other compounds.

[0159] compound molar extinction coefficient Solubility in dichloromethane Redox peak logarithm B2 <![CDATA[248000M -１ cm -1 ]]> greater than 60 mg / mL 2 pairs B13 <![CDATA[302000M -１ cm -1 ]]> greater than 60 mg / mL 2 pairs B15 <![CDATA[310000M -１ cm -1 ]]> greater than 60 mg / mL 2 pairs B18 290000M-1cm-1 greater than 60 mg / mL 2 pairs B21 280000M-1cm-1 greater than 60 mg / mL 2 pairs B22 369000M-1cm-1 greater than 60 mg / mL 2 pairs B28 320000M-1cm-1 greater than 60 mg / mL 2 pairs

[0160] The data in the table show that compounds B2, B13, B15, B18, B21, B22, and B28 also have excellent light-harvesting properties, high solubility, and good redox properties.

[0161] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any person skilled in the art can make some changes or modifications to the above-described technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A class of naphthodioxazine imide compounds, characterized in that, The compound has the following general structural formula: Wherein: R is independently selected from groups containing substituents or not containing substituents, and the groups containing substituents or not containing substituents are selected from C1-C30 fluoroalkyl, C3-C30 fluorocycloalkyl, and C1-C30 fluoroalkoxy groups containing substituents or not containing substituents. The substituents are selected from C1-C16 alkyl groups and C1-C16 fluoroalkyl groups.

2. The naphthodioxazine imide compound according to claim 1, characterized in that, The substituents or unsubstituents are C1-C20 fluoroalkyl groups, C1-C20 fluoroalkoxy groups, and C4-C20 fluorocycloalkyl groups.

3. The naphthodioxinimide compound according to claim 1 or 2, characterized in that, The substituents are C1-C16 alkyl groups or C1-C16 fluoroalkyl groups.

4. The naphthodioxazine imide compound according to claim 1, characterized in that, The groups containing or not containing substituents are C1-C30 perfluoroalkyl groups or C1-C30 semifluorinated alkyl groups.

5. The method for preparing a class of naphthodioxazine imide compounds according to claim 1, characterized in that, Compound A was mixed with dihydroxybenzoquinone and heated to react, yielding the naphthodioxinimide compound, as shown in the following reaction formula: The definition of R is the same as that in claim 1.

6. The method for preparing a class of naphthodioxazine imide compounds according to claim 5, characterized in that, The preparation method involves heating at a temperature of 90-120℃, reacting for 6-12 hours, and using a molar ratio of compound A to dihydroxybenzoquinone of 2.1-2.

5.

7. The application of the naphthodioxazine imide compound according to claim 1 as an optoelectronic material in the field of organic semiconductor materials.

8. The application of the naphthodioxazine imide compound according to claim 1 in the fields of solar cells, light-emitting diodes, organic thermoelectric devices, and organic field-effect transistors.

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