CN102617572A - Tetracene-5,6:11,12-tetrabasic carboxylic acid diimide compound and preparation method thereof - Google Patents

Abstract

The present invention relates to the naphthacene-5,6:11,12-tetracarboxylic acid diimide compound of the following formula I, and the preparation method of the compound, wherein: R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ , the same or different, independently represent hydrogen, substituted or unsubstituted, C1-30 alkyl, C1-30 alkoxy, C3- 30 cycloalkyl, C5-30 aryl, C1-30 alkyl aryl, C1-30 alkyl heteroaryl, C1-30 alkyl heterocyclyl, C1-30 alkylene oxyalkyl, C1- 30 alkyleneoxyaryl, C1-30 alkyleneoxyheteroaryl, C1-30 alkyleneoxyheterocyclic.

Description

Naphthacene-5,6:11,12-tetracarboxylic acid diimides and preparation method thereof

technical field

The present invention relates to naphthacene-5,6:11,12-tetracarboxylic acid diimide compound and the preparation method of the compound, and also relates to naphthacene-5,6:11,12-tetracarboxylic diimide Application of imide compounds as light-absorbing materials and electron-transporting materials in organic electroluminescent devices, organic thermochromic elements, organic field-effect transistors, and organic solar cells.

Background technique

Because of the large conjugated system, acenes have been found to have good charge transport properties, and have shown good field effect performance and are used in flexible electronic devices ( Chem. Rev. 2004, 104 , 4891; Ad v . Mater . 2002, 14 , 99.) have potential applications. Anthracene is the smallest acene-type field effect material reported so far, and its single crystal mobility is about 0.02 cm ² /Vs when the temperature is low ( Appl. Phys. Lett. 2004, 84 , 5383-5385.) . On the octadecylchlorosilane (ODTS) modified SiO ₂ substrate, the mobility of tetracene thin film ( Appl. Phys. Lett. 2002, 80 , 2925-2927.) reaches 0.1 cm ² /Vs, and its single crystal ( J. Appl. Phys. 2004, 96 , 2080-2086.) The mobility can reach 1.3 cm ² /Vs, and the on/off ratio can reach as high as 10 ⁶ .

So far, there are only two types of reports on the modification of tetracene, one is rubrene, which is the star molecule in the derivatives of naphthacene, although the four benzene ring substituents of rubrene make the whole molecule and It is not a coplanar system, but the four side substituents make a large π-π overlap between the central cores of adjacent molecules ( Science. 2004, 303 , 1644-1646.). The other is a series of tetracene-based halides synthesized by Zhenan Bao et al. It is found that the number of halogens is closely related to the packing of molecules, the compound substituted by a single halogen presents a fishbone-like packing, and the compound substituted by two halogens presents a slip π stacking. Field-effect transistors based on β-based FETs show a wide range of mobilities, with dibromo-substituted mobilities as high as 1.6 cm ² /Vs, possibly attributable to their larger π-overlap. ( J. Am. Chem. Soc. 2004, 126 , 15322-15323.).

The inventors of the present invention have found that high-mobility N-type materials can be obtained by functionalizing traditional P-type cores with strong electron-withdrawing substituents, such as perfluoro-substituted pentacene ( J. Am. Chem. Soc. 2004, 126 , 8138-8140), all the hydrogens of pentacene were replaced by electron-withdrawing fluorine atoms, on the one hand, the stability of pentacene was improved, and on the other hand, perfluoropentacene exhibited N-type organic Semiconductor properties, similarly, strong electron-withdrawing imide functionalized perylene and naphthalene, namely peryleneimide ( Angew. Chem. Int. Ed. 2010, 49 , 740-743 ) and naphthalimide ( Nature , 2000, 404 , 478-481), all exhibit excellent N-type field effect properties and have been extensively studied.

However, there is still a need in the art to obtain strongly electron-withdrawing imide-substituted naphthacene-5,6:11,12-tetracarboxylic acid diimides, in particular, there is still a need in the art to obtain a class of Tetraphenyl-5,6:11,12-tetracarboxylic acid diimide compounds, which can be placed in the air for several weeks, and their UV absorption peaks do not change, that is, they have very good stability, and should be used as Air-stable n-type electron transport materials. In addition, there is still a need in the art for the aforementioned naphthacene-5,6:11,12-tetracarboxylic diimides to have broad absorption in visible light and near-infrared (350-830 nm). Furthermore, there is still a need in the art for a simple and efficient preparation method for synthesizing the above compounds, and a preparation method with a higher yield.

Contents of the invention

One object of the present invention is to provide naphthacene-5,6:11,12-tetracarboxylic acid diimides. Another object of the present invention is to provide a method for preparing the above-mentioned object compound.

The present invention relates to naphthacene-5,6:11,12-tetracarboxylic acid diimide compound, which has the following formula I structure:

in:

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ , the same or different, independently represent hydrogen, substituted or unsubstituted, C1-30 Alkyl, C1-30 alkoxy, C3-30 cycloalkyl, C5-30 aryl, C1-30 alkylaryl, C1-30 alkyl heteroaryl, C1-30 alkyl heterocyclic, C1 -30 alkyleneoxyalkyl, C1-30 alkyleneoxyaryl, C1-30 alkyleneoxyheteroaryl, C1-30 alkyleneoxyheterocyclic,

Wherein, optionally, _R3 and _R4 form together, substituted or unsubstituted, C3-30 cycloalkyl, C5-30 aryl, C1-30 alkylaryl, C1-30 alkylheteroaryl , C1-30 alkylene heterocyclic group, C1-30 alkylene oxyaryl group, C1-30 alkylene oxyheteroaryl group, C1-30 alkylene oxyheterocyclic group,

Wherein, optionally, R ₈ and R ₉ form together, substituted or unsubstituted, C3-30 cycloalkyl, C5-30 aryl, C1-30 alkylaryl, C1-30 alkylheteroaryl , C1-30 alkylene heterocyclic group, C1-30 alkylene oxyaryl group, C1-30 alkylene oxyheteroaryl group, C1-30 alkylene oxyheterocyclic group,

Provided that R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₈ , R ₉ and R ₁₀ are not simultaneously hydrogen.

In one embodiment of the compound of the present invention, _R3 and _R4 can form together, or _R8 and _R9 can form together, the following groups: substituted or unsubstituted, C3-30 cycloalkyl, C5 -30 aryl, C1-30 alkyl aryl, C1-30 alkyl heteroaryl, C1-30 alkyl heterocyclic, C1-30 alkylene oxyaryl, C1-30 alkylene oxy Heteroaryl, C1-30 alkyleneoxy heterocyclic group.

In another embodiment of said compounds of the present invention, aryl is selected from, substituted or unsubstituted, phenyl, naphthyl, anthracenyl, phenanthrenyl, naphthacene, pentacene, hexaphenyl , pyrenyl, indenyl, biphenyl, fluorenyl.

噻、吡咯、咪唑、吡唑、吡啶、吡嗪、嘧啶、哒嗪、吲嗪、吲哚、异吲哚基、吲唑、嘌呤、喹嗪、喹啉、酞嗪、萘啶、喹喔啉、蝶啶、咔唑、咔啉、菲啶、菲咯啉、吖啶、吩嗪、噻唑、吩噻嗪、

唑、吩

嗪、

唑基、

二唑基、呋咱基、二噻吩并吡咯、三并噻吩、苯并

唑基, 苯并咪唑基, 苯并噻吩, 苯并噻唑基、苯并噻吩、苯并呋喃、苯并吡喃、苯并吩噻、苯并吡咯、苯并咪唑、苯并吡唑、苯并吡啶、苯并吡嗪、苯并嘧啶、苯并哒嗪、苯并吲嗪、苯并吲哚、苯并吲唑、苯并嘌呤、苯并喹嗪、苯并喹啉、苯并酞嗪、苯并萘啶、苯并喹喔啉、苯并蝶啶、苯并咔唑、苯并咔啉、苯并菲啶、苯并菲咯啉、苯并吖啶、苯并吩嗪、苯并噻唑、苯并吩噻嗪、苯并

唑、苯并吩

嗪、或上述基团的环与上述权利要求2所定义芳基的环稠合衍生的基团，或上述基团的组合。这些取代基中的每一个可以另外被取代。 In another embodiment of said compound of the present invention, the heterocyclic group is selected from, substituted or unsubstituted, thiophene, furan, pyran, phen

Thiothia, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, indole, isoindolyl, indazole, purine, quinozine, quinoline, phthalazine, naphthyridine, quinoxaline , pteridine, carbazole, carboline, phenanthridine, phenanthroline, acridine, phenazine, thiazole, phenothiazine,

Azole, phen

Zinc,

Azolyl,

Diazolyl, Furazanyl, Dithienopyrrole, Trithiophene, Benzo

Azolyl, Benzimidazolyl, Benzothiophene, Benzothiazolyl, Benzothiophene, Benzofuran, Benzopyran, Benzophene Thiothia, benzopyrrole, benzimidazole, benzopyrazole, benzopyridine, benzopyrazine, benzopyrimidine, benzopyridazine, benzoinzine, benzoindole, benzoindazole, benzo Purine, benzoquinazine, benzoquinoline, benzophthalazine, benzonaphthyridine, benzoquinoxaline, benzopteridine, benzocarbazole, benzocarboline, benzophenanthridine, benzo phenanthroline, benzoacridine, benzophenazine, benzothiazole, benzophenothiazine, benzo

Azole, Benzophene

A group derived from oxazine, or the ring of the above-mentioned group fused with the ring of the aryl group defined in claim 2 above, or a combination of the above-mentioned groups. Each of these substituents may be additionally substituted.

In another embodiment of said compound of the present invention, the alkyl group is selected from, substituted or unsubstituted methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl Base, Pentyl, Hexyl, Heptyl, Octyl, Nonyl, Decyl, Undecyl, Dodecyl, Tridecyl, Tetradecyl, Pentadecyl, Decyl Hexadecyl, Heptadecanyl, Octadecanyl, Nonadecanyl and Eicosyl.

In another embodiment of said compounds of the present invention, alkoxy is selected from the group consisting of, substituted or unsubstituted methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy , isobutoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tendecyloxy Tricarbonyloxy, tetradecyloxy, pentadecyloxy, hexadecanyloxy, heptadecanyloxy, octadecyloxy, ninedecyloxy and twenty carbon alkoxy.

In another embodiment of said compound of the present invention, the alkylene group is selected from, substituted or unsubstituted methylene, ethylene, propylene, isopropylidene, n-butylene, sec-butylene , Isobutylene, tert-butylene, Pentylene, Hexylene, Heptylene, Octylene, Nonylene, Decylene, Undecylene, Dodecylene, Decylene Tricarbonyl, tetradecylene, pentadecylene, hexadecanylene, heptadecanylene, octadecylene, nonadecenylene and eicosylene carbon alkyl.

In another embodiment of said compound of the present invention, cycloalkyl is selected from, substituted or unsubstituted cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl , Undecylcycloalkyl, Dodecylcycloalkyl, Tridecylcycloalkyl, Tetradecylcycloalkyl, Pentadecylcycloalkyl, Hexadecylcycloalkyl, Seventeen-carboncycloalkyl, Octadecylcycloalkyl, nineadecylcycloalkyl and eicoscycloalkyl.

In another embodiment of said compounds of the present invention, heteroaryl is selected from, substituted or unsubstituted, pyrrolyl, pyrazinyl, pyridyl, indolyl, isoindolyl, furyl, benzofuran Base, , isobenzofuryl, quinolinyl, 1-isoquinolyl, quinoxalinyl, carbazolyl, phenanthridinyl, acridinyl, o-diazaphenanthrenyl, phenazinyl, phenothione Azinyl, phenothiazinyl, phen Azinyl, Azolyl, furanyl, thienyl.

In another embodiment of the compounds of the present invention, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ , the same or different, independently represent Halogenated C1-30 alkyl, preferably, perhalogenated C1-30 alkyl, which is preferably substituted by fluorine, chlorine, bromine, iodine.

In another embodiment of said compound of the present invention, said substituent is selected from:

- alkyl, which has 1-16 carbon atoms,

- alkoxy, which has 1-16 carbon atoms,

- aryl, which has 5-16 carbon atoms,

- cycloalkyl, which has 3-16 carbon atoms,

-Heterocyclic group, which has 5-16 carbon atoms, the heteroatom T group contained in the group is selected from B, Si, Sn, N, O, S and Se;

-heteroaryl, which has 1-16 carbon atoms,

- Aralkyl groups having 5-16 carbon atoms, wherein the alkyl moiety has 1-16 carbon atoms.

In another embodiment of said compound of the present invention, said substituent is selected from:

- Alkyl groups such as methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl ;

- cycloalkyl, such as cyclopropyl, cyclopentyl, or cyclohexyl;

- alkenyl, such as vinyl, allyl, 2-butenyl, or 3-pentenyl;

-alkynyl, such as propargyl or 3-pentynyl,

- aryl, such as phenyl, p-methylphenyl, naphthyl or anthracenyl;

-amino group, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, or xylylamino;

- alkoxy, such as methoxy, ethoxy, butoxy or 2-ethylhexyloxy;

-Aryloxy, such as phenyloxy, 1-naphthyloxy, or 2-naphthyloxy;

-heteroaryloxy, such as pyridyloxy, pyrazolyloxy, pyrimidinyloxy or quinolinyloxy;

- an acyl group such as acetyl, benzoyl, formyl or pivaloyl;

- alkoxycarbonyl, such as methoxycarbonyl or ethoxycarbonyl;

- aryloxycarbonyl, such as phenyloxycarbonyl;

- acyloxy, such as acetoxy or benzoyloxy;

- an amido group, such as acetamido or benzoylamino;

- alkoxycarbonylamino, such as methoxycarbonylamino;

- aryloxyoxyamino, such as phenyloxycarbonylamino;

- sulfonylamino, such as methanesulfonylamino or benzenesulfonylamino;

- sulfamoyl, such as aminosulfonyl, methylaminosulfonyl, dimethylsulfamoyl, or phenylaminosulfonyl;

- carbamoyl, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, or phenylcarbamoyl;

- Alkylthio, such as methylthio or ethylthio;

-Arylthio, such as phenylthio;

唑基硫基，或2-苯并噻唑基硫基；  -Heteroarylthio, such as pyridylthio, 2-benzimidazolylthio, 2-benzo

Azolylthio, or 2-benzothiazolylthio;

-sulfonyl, such as methylsulfonyl or toluenesulfonyl;

- sulfinyl, such as methylsulfinyl or phenylsulfinyl;

- ureido, such as ureido, methylureido or phenylureido;

- Phosphoric amido groups, such as diethylphosphoramide or phenylphosphoramide;

- Hydroxy;

- mercapto;

- a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom);

- cyano;

- sulfo group;

-carboxyl;

- nitro;

- hydroxamic acid group;

- sulfinyl group;

- hydrazino;

- imino group;

唑基，苯并咪唑基，和苯并噻唑基； - Heterocyclic groups such as imidazolyl, pyridyl, quinolinyl, furyl, thienyl, piperidyl, morpholino, benzo

Azolyl, benzimidazolyl, and benzothiazolyl;

- a silyl group, such as trimethylsilyl or triphenylsilyl.

In another said compound embodiment of the invention, said compound is:

，

，

,

,

， or

,

Wherein Et represents ethyl, and Bu represents butyl.

The present invention also relates to the method for preparing above-mentioned compound, it comprises the following steps:

1). Reaction of the halogenated metallocene reagent Cp ₂ LX ₂ with the alkyne compound B to obtain the compound of formula II and/or formula III:

and / or

in,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different,

Defined as defined above,

Cp represents cyclopentadienyl or known as cyclopentadienyl,

L represents the IVA or IVB group metals in the periodic table of elements, such as zirconium or titanium,

X represents halogen, such as fluorine, chlorine, bromine, iodine,

B represents an alkyne compound, such as R≡R', RC≡C-(CH ₂ ) _n -C≡C-R'', or RC≡C-(CH ₂ ) _n -C≡C-(CH ₂ ) _n - C≡C-R''', wherein R, R', R'' and R''', the same or different, represent R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , A group defined by R ₇ , R ₈ , R ₉ or R ₁₀ or another suitable protecting group, such as a trihydrocarbylsilyl group such as trimethylsilyl, triisopropylsilyl or triphenylsilyl, or Aryl such as phenyl; n=3,4,5,6,7,8,9 or 10;

2). The compound of formula IV tetrahalogenated tetracarboxylic naphthalene diimide reacts with the compound of formula II and or formula III obtained in the previous step to obtain the compound of formula I:

in,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different,

Defined as defined above,

X, same or different, represents halogen, such as fluorine, chlorine, bromine, iodine.

In another embodiment of the preparation method of the compound of the present invention, in view of the stability of the compound of formula II and/or formula III in step 1) of the above preparation method, preferably, R ₂ , R ₅ , R ₇ and R ₁₀ does not represent hydrogen at the same time.

In another embodiment of the preparation method of the compound of the present invention, the tetrahalogenated tetracarboxylic naphthalene diimide compound of the present invention is 2,3:6,7-tetrahalogen with or without substituents Chloronaphthalene-5,6:11,12-tetracarboxylic diimide compound, 2,3:6,7-tetrabromonaphthalene-5,6:11,12-tetracarboxylic diimide compound. The substituent is hydrogen, C ₁ -C ₃₀ perfluoroalkyl, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy or substituted or unsubstituted aryl.

In one embodiment of the preparation method of the compound of the present invention, in step 1), a solvent is added to the compound of formula VI, and the ratio of the compound of formula VI to the solvent is 0.01-1.0 mmol/ml.

In another embodiment of the preparation method of the compound of the present invention, the molar ratio of the tetrahalogenated tetracarboxylic acid naphthalene diimide compound to the compound of formula VI is 1:1-10.

In another embodiment of the compound preparation method of the present invention, a catalyst is added to the product of step 1), and the molar ratio of the catalyst to the tetrahalogenated tetracarboxylic naphthalene diimide compound is 10:1-1.

In another embodiment of the preparation method of the compound of the present invention, the reaction temperature is controlled at 0°C to 70°C.

In another embodiment of the preparation method of the compound of the present invention, the catalyst is cuprous chloride.

Specifically, the preparation method of the naphthacene-5,6:11,12-tetracarboxylic diimide compound of the present invention comprises the following steps:

(1). Under the protection of an inert gas, add tetrahydrofuran to the zirconium reagent, and the ratio of the zirconium reagent to the solvent is 0.01-1.0 mmol/ml;

(2). Add 2,3:6,7-tetrahalogenated tetracarboxylic naphthalimides to the mixture prepared in step (1). The molar ratio of 2,3:6,7-tetrahalogenated tetracarboxylic naphthalimide to zirconium reagent is 1:2～10.

(3). Add a catalyst to the mixture prepared in step (2), the molar ratio of catalyst to 2,3:6,7-tetrahalogenated tetracarboxylic naphthalimide compound is 10:1~1, react The temperature is controlled at 0°C to 70°C, preferably 55°C.

(4). After the reaction is completed, the product is extracted with organic solvents such as dichloromethane, ethyl acetate or toluene, dried with a desiccant, evaporated to dryness, separated and purified to obtain naphthacene-5,6:11,12-tetracarboxylic acid di imide compounds.

In another embodiment of the preparation method of the compound of the present invention, the inert gas includes nitrogen or argon.

In another embodiment of the preparation method of the compound of the present invention, the organic solvent used in the extraction is dichloromethane, ethyl acetate or toluene.

In another embodiment of the preparation method of the compound of the present invention, the temperature in step (1) is 0°C to 70°C.

The yield of the target product obtained in the present invention after separation and purification is 40%-55%. The obtained compound was confirmed by nuclear magnetic resonance spectrum ( ¹ H-NMR) and mass spectrum (MS), as shown in the accompanying drawing.

The raw materials used in the present invention can be purchased from the market or synthesized according to the prior art; as the zirconium reagent is according to the literature ( J. Am. Chem. Soc.; 1989, 111, 3336-3346; J. Am. Chem . Soc.; 1987, 109, 2788-2796.; J. Am. Chem. Soc.; 1989, 111, 2870-2874; J. Org. Chem. , 1995, 60, 4444 ) reported method synthesis; 2,3:6,7-tetrahalogenated tetracarboxylic naphthalene diimides are based on literature ( J. Org. Chem. , 2007, 72, 8070-8075; Org. Lett., 2007, 9, 3917-3920) synthesized by the method reported.

The invention also relates to the application of the above-mentioned compound as a light-absorbing material and an electron-transporting material in organic electroluminescent devices, organic thermochromic elements, organic field-effect transistors, and organic solar cells.

The present invention also relates to an organic electroluminescent device, an organic thermochromic element, an organic field effect transistor or an organic solar cell, which comprise the aforementioned compound.

Examples of aryl groups useful in the compounds of the present invention include, but are not limited to, phenyl, naphthyl, anthracenyl, phenanthrenyl, naphthacene, pentacene, hexaphenyl, pyrenyl, indenyl, biphenyl Base, o-tolyl, m-tolyl, p-tolyl, p-tert-butylphenyl, p-(2-phenylpropyl)phenyl, 3-methyl-2-naphthyl, 4- Methyl-1-naphthyl, 4-methyl-1-anthracenyl, 4'-methylbiphenyl, 4"-tert-butyl-p-terphenyl-4-yl, 9,9-dimethyl Fluoren-1-yl, 9,9-dimethylfluoren-2-yl, 9,9-dimethylfluoren-3-yl, and 9,9-dimethylfluoren-4-yl. Other examples include the Substituents for combinations of phenyl, phenylene, naphthyl and naphthylene (such as phenylnaphthyl, naphthylphenyl, naphthylnaphthyl, naphthylnaphthylnaphthyl, phenylphenylnaphthyl, Naphthylnaphthylphenyl, naphthylphenylnaphthyl, naphthylphenylphenyl, phenylnaphthylnaphthyl, and phenylnaphthylphenyl). From substituted or unsubstituted Groups formed by substituting an aryl group are preferred.In particular, phenyl, naphthyl and phenanthrenyl are preferred.

Examples of alkyl groups useful in the compounds of the present invention include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl radical, n-heptyl, n-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecanyl Heptadecanyl, Octadecanyl, Nonadecanyl and Eicosyl, Hydroxymethyl, 1-Hydroxyethyl, 2-Hydroxyethyl, 2-Hydroxyisobutyl, 1 ,2-dihydroxyethyl, 1,3-dihydroxyisopropyl, 2,3-dihydroxy-tert-butyl, 1,2,3-trihydroxypropyl, chloromethyl, 1-chloroethyl, 2-chloroethyl, 2-chloroisobutyl, 1,2-dichloroethyl, 1,3-dichloroisopropyl, 2,3-dichloro-tert-butyl, 1,2,3-tri Chloropropyl, bromomethyl, 1-bromoethyl, 2-bromoethyl, 2-bromoisobutyl, 1,2-dibromoethyl, 1,3-dibromoisopropyl, 2,3- Dibromo-tert-butyl, 1,2,3-tribromopropyl, monoiodomethyl, 1-iodoethyl, 2-iodoethyl, 2-iodoisobutyl, 1,2-diiodoethyl , 1,3-diiodoisopropyl, 2,3-diiodo-tert-butyl, 1,2,3-triiodopropyl, monoaminomethyl, 1-aminoethyl, 2-aminoethyl, 2-aminoisobutyl, 1,2-diaminoethyl, 1,3-diaminoisopropyl, 2,3-diamino-tert-butyl, 1,2,3-triaminopropyl, cyano Methyl, 1-cyanoethyl, 2-cyanoethyl, 2-cyanoisobutyl, 1,2-dicyanoethyl, 1,3-dicyanoisopropyl, 2,3- Dicyano-tert-butyl, 1,2,3-tricyanopropyl, nitromethyl, 1-nitroethyl, 2-nitroethyl, 2-nitroisobutyl, 1,2 - dinitroethyl, 1,3-dinitroisopropyl, 2,3-dinitro-tert-butyl, and 1,2,3-trinitropropyl.

噻基、吡咯基、咪唑基、吡唑基、吡啶基、吡嗪基、嘧啶基、哒嗪基、吲嗪基、吲哚基、吲唑基、嘌呤基、喹嗪基、喹啉基、酞嗪基、萘啶基、喹喔啉基、蝶啶基、咔唑基、咔啉基、菲啶基、菲咯啉基、吖啶基、吩嗪基、噻唑基、吩噻嗪基、

唑基、吩嗪基、二噻吩并吡咯基、三并噻吩基、苯并

唑基基, 苯并咪唑基, 苯并噻吩基, 苯并噻唑基、苯并噻吩基、苯并呋喃基、苯并吡喃基、苯并吩

噻基、苯并吡咯基、苯并咪唑基、苯并吡唑基、苯并吡啶基、苯并吡嗪基、苯并嘧啶基、苯并哒嗪基、苯并吲嗪基、苯并吲哚基、苯并吲唑基、苯并嘌呤基、苯并喹嗪基、苯并喹啉基、苯并酞嗪基、苯并萘啶基、苯并喹喔啉基、苯并蝶啶基、苯并咔唑基、苯并咔啉基、苯并菲啶基、苯并菲咯啉基、苯并吖啶基、苯并吩嗪基、苯并噻唑基、苯并吩噻嗪基、苯并唑基、苯并吩

嗪基、或上述基团的环与上述芳基的环、上述杂环基的环和/或上述杂芳基的环稠合衍生的基团，或上述基团的组合。这些取代基中的每一个可以另外被取代。 Examples of heterocyclic groups useful in compounds of the present invention include, but are not limited to, thienyl, furyl, pyranyl, phen

Thiyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, indolyl, indazolyl, purinyl, quinozinyl, quinolinyl, Phthalazinyl, naphthyridinyl, quinoxalinyl, pteridinyl, carbazolyl, carbolinyl, phenanthridinyl, phenanthrolinyl, acridinyl, phenazinyl, thiazolyl, phenothiazinyl,

Azolyl, phen Azinyl, dithienopyrrolyl, trithienyl, benzo

Azolyl, Benzimidazolyl, Benzothienyl, Benzothiazolyl, Benzothienyl, Benzofuryl, Benzopyranyl, Benzophene

Thiyl, benzopyrrolyl, benzoimidazolyl, benzopyrazolyl, benzopyridyl, benzopyrazinyl, benzopyrimidinyl, benzopyridazinyl, benzoindolizinyl, benzoin Indolyl, benzoindazolyl, benzopurinyl, benzoquinazinyl, benzoquinolinyl, benzophthalazinyl, benzonaphthyridinyl, benzoquinoxalinyl, benzopteridinyl , benzocarbazolyl, benzocarbolinyl, benzophenanthridinyl, benzophenanthrolinyl, benzoacridinyl, benzophenazinyl, benzothiazolyl, benzophenothiazinyl, Benzo Azolyl, benzophene

An azinyl group, or a group derived from the fusion of the ring of the above-mentioned group with the ring of the above-mentioned aryl group, the ring of the above-mentioned heterocyclic group and/or the ring of the above-mentioned heteroaryl group, or a combination of the above-mentioned groups. Each of these substituents may be additionally substituted.

唑基，苯并咪唑基，和苯并噻唑基)；和甲硅烷基(具有优选3-40个，更优选3-30个，或特别优选3-24个碳原子，如三甲基甲硅烷基或三苯基甲硅烷基)。这些取代基中的每一个可以另外被取代。 Examples of substituents further substituting each group in each of the compounds of the present invention include: alkyl (having preferably 1-30, more preferably 1-20, such as methyl, ethyl, isopropyl, tert-butyl , n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl); cycloalkyl (with preferably 3-30, more preferably 3-20 , or particularly preferably 3-10 carbon atoms, such as cyclopropyl, cyclopentyl, or cyclohexyl); alkenyl (having preferably 2-30, more preferably 2-20, or particularly preferably 2-10 carbon atoms, such as vinyl, allyl, 2-butenyl, or 3-pentenyl); alkynyl (having preferably 2-30, more preferably 2-20, or particularly preferably 2-10 carbon atoms, such as propargyl or 3-pentynyl), aryl (with preferably 6-30, more preferably 6-20, or particularly preferably 6-12 carbon atoms, such as phenyl, p-methyl phenyl, naphthyl or anthracenyl); amino group (having preferably 0-30, more preferably 0-20, or particularly preferably 0-10 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino ylamino, dibenzylamino, diphenylamino, or xylylamino); alkoxy (having preferably 1-30, more preferably 1-20, or particularly preferably 1-10 carbon atoms, such as methyl oxy, ethoxy, butoxy or 2-ethylhexyloxy); aryloxy (having preferably 6-30, more preferably 6-20, or particularly preferably 6-12 carbon atoms, such as benzene yloxy, 1-naphthyloxy, or 2-naphthyloxy); heteroaryloxy (having preferably 1-30, more preferably 1-20, or particularly preferably 1-12 carbon atoms, such as pyridyl oxy, pyrazolyloxy, pyrimidinyloxy or quinolinyloxy); acyl (having preferably 1-30, more preferably 1-20, or particularly preferably 1-12 carbon atoms, such as acetyl , benzoyl, formyl or pivaloyl); alkoxycarbonyl (having preferably 2-30, more preferably 2-20, or particularly preferably 2-12 carbon atoms, such as methoxycarbonyl or ethoxy ylcarbonyl); aryloxycarbonyl (having preferably 7-30, more preferably 7-20, or particularly preferably 7-12 carbon atoms, such as phenyloxycarbonyl); acyloxy (having preferably 2-30 , more preferably 2-20, or particularly preferably 2-10 carbon atoms, such as acetoxy or benzoyloxy); amido (with preferably 2-30, more preferably 2-20, or particularly preferably 2-10 carbon atoms, such as acetylamino or benzoylamino); alkoxycarbonylamino (with preferably 2-30, more preferably 2-20, or particularly preferably 2-12 carbon atoms, such as methyl oxycarbonylamino); aryloxyoxyamino (having preferably 7-30, more preferably 7-20, or particularly preferably 7-12 carbon atoms, such as phenyloxycarbonylamino); sulfonylamino ( Having preferably 1-30, more preferably 1-20, or particularly preferably 1-12 carbon atoms, such as methanesulfonylamino or benzenesulfonylamino); sulfamoyl (with preferred 0-30, more preferably 0-20, or particularly preferably 0-12 carbon atoms, such as aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, or phenylaminosulfonyl); Aminomethyl Acyl (having preferably 1-30, more preferably 1-20, or particularly preferably 1-12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, or phenylcarbamoyl ); alkylthio (having preferably 1-30, more preferably 1-20, or particularly preferably 1-12 carbon atoms, such as methylthio or ethylthio); arylthio (having preferably 6-30 , more preferably 6-20, or particularly preferably 6-12 carbon atoms, such as phenylthio); heteroarylthio (with preferably 1-30, more preferably 1-20, or particularly preferably 1-12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzo Azolylthio, or 2-benzothiazolylthio); sulfonyl (having preferably 1-30, more preferably 1-20, or particularly preferably 1-12 carbon atoms, such as methylsulfonyl or toluenesulfonyl acyl); sulfinyl (with preferably 1-30, more preferably 1-20, or particularly preferably 1-12 carbon atoms, such as methylsulfinyl or phenylsulfinyl); ureido (with preferably 1 -30, more preferably 1-20, or particularly preferably 1-12 carbon atoms, such as ureido, methylureido or phenylureido); Phosphate amido group (with preferably 1-30, more preferably 1 -20 or particularly preferably 1-12 carbon atoms, such as diethylphosphoramide or phenylphosphoramide); hydroxyl; mercapto; halogen atom (such as fluorine atom, chlorine atom, bromine atom, or iodine atom); ; sulfo; carboxyl; nitro; hydroxamic acid group; sulfinyl; hydrazino; imino; heterocyclic group (having preferably 1-30 or preferably 1-12 carbon atoms and containing For example nitrogen atom, oxygen atom or sulfur atom, and specific examples include imidazolyl, pyridyl, quinolinyl, furyl, thienyl, piperidyl, morpholino, benzo

Azolyl, benzimidazolyl, and benzothiazolyl); and a silyl group (having preferably 3-40, more preferably 3-30, or particularly preferably 3-24 carbon atoms, such as trimethylsilyl group or triphenylsilyl). Each of these substituents may be additionally substituted.

Examples of the alkoxy group used in the present invention include, but are not limited to, wherein the alkyl moiety has the same definition as the above-mentioned alkyl group, such as ethylmethyloxy, ethyloxy, propyloxy, isopropyloxy , n-butyloxy, s-butyloxy, isobutyloxy, tert-butyloxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n- Octyloxy, Hydroxyethylmethyloxy, 1-Hydroxyethyloxy, 2-Hydroxyethyloxy, 2-Hydroxyisobutyloxy, 1,2-Dihydroxyethyloxy, 1 ,3-dihydroxyisopropyloxy, 2,3-dihydroxy-tert-butyloxy, 1,2,3-trihydroxypropyloxy, chloroethylmethyloxy, 1-chloroethyl Oxyloxy, 2-Chloroethyloxy, 2-Chloroisobutyloxy, 1,2-Dichloroethyloxy, 1,3-Dichloroisopropyloxy, 2,3-Dichloro -tert-butyloxy, 1,2,3-trichloropropyloxy, bromoethylmethyloxy, 1-bromoethyloxy, 2-bromoethyloxy, 2-bromoisobutyl 1,2-dibromoethyloxy, 1,3-dibromoisopropyloxy, 2,3-dibromo-tert-butyloxy, 1,2,3-tribromopropane yloxy, iodoethylmethyloxy, 1-iodoethyloxy, 2-iodoethyloxy, 2-iodoisobutyloxy, 1,2-diiodoethyloxy, 1, 3-Diiodoisopropyloxy, 2,3-Diiodo-tert-Butyloxy, 1,2,3-Triiodopropyloxy, Aminoethylmethyloxy, 1-Aminoethyl Oxygen, 2-aminoethyloxy, 2-aminoisobutyloxy, 1,2-diaminoethyloxy, 1,3-diaminoisopropyloxy, 2,3-diamino- tert-Butyloxy, 1,2,3-triaminopropyloxy, cyanoethylmethyloxy, 1-cyanoethyloxy, 2-cyanoethyloxy, 2-cyano Isobutyloxy, 1,2-dicyanoethyloxy, 1,3-dicyanoisopropyloxy, 2,3-dicyano-tert-butyloxy, 1,2 ,3-tricyanopropyloxy, nitroethylmethyloxy, 1-nitroethyloxy, 2-nitroethyloxy, 2-nitroisobutyloxy, 1, 2-Dinitroethyloxy, 1,3-Dinitroisopropyloxy, 2,3-Dinitro-tert-butyloxy, 1,2,3-Trinitropropyloxy base.

Description of drawings

Figure 1. 1,2,3,4,7,8,9,10-octa(ethyl)-N,N'-di(n-octyl)-tetracene-5,6 of Example 1 of the present invention : Mass spectrum of 11,12-tetracarboxylic diimide.

Figure 2. 1,2,3,4,7,8,9,10-octa(ethyl)-N,N'-di(n-octyl)-tetracene-5,6 of Example 1 of the present invention : ¹ H-NMR chart of 11,12-tetracarboxylic diimide.

Figure 3. 1,2,3,4,7,8,9,10-octa(ethyl)-N,N'-di(n-octyl)-tetracene-5,6 of Example 1 of the present invention : Absorption diagram of 11,12-tetracarboxylic diimide.

Figure 4. 1,2,3,4,7,8,9,10-octa(ethyl)-N,N'-di(n-octyl)-tetracene-5,6 of Example 1 of the present invention : Electrochemical diagram of 11,12-tetracarboxylic diimide.

Figure 5. 1,2,3,4,7,8,9,10-octa(ethyl)-N,N'-di(2,2,3,3,4,4, Mass spectrum of 4-heptafluoro-n-butyl)-tetracene-5,6:11,12-tetracarboxylic diimide.

Figure 6. 1,2,3,4,7,8,9,10-octa(ethyl)-N,N'-di(2,2,3,3,4,4, ¹ H-NMR chart of 4-heptafluoro-n-butyl)-tetracene-5,6:11,12-tetracarboxylic acid diimide.

Figure 7. 1,2,3,4,7,8,9,10-octa(ethyl)-N,N'-di(2,2,3,3,4,4, Absorption pattern of 4-heptafluoro-n-butyl)-tetracene-5,6:11,12-tetracarboxylic diimide.

Figure 8. 1,2,3,4,7,8,9,10-octa(ethyl)-N,N'-di(2,2,3,3,4,4, Electrochemical diagram of 4-heptafluoro-n-butyl)-tetracene-5,6:11,12-tetracarboxylic acid diimide.

Figure 9. 1,2,3,4,7,8,9,10-octa(n-butyl)-N,N'-di(n-octyl)-tetracene-5 of Example 3 of the present invention, 6: The mass spectrum of 11,12-tetracarboxylic diimide.

Figure 10. 1,2,3,4,7,8,9,10-octa(n-butyl)-N,N'-di(n-octyl)-tetracene-5 of Example 3 of the present invention, 6: ¹ H-NMR chart of 11,12-tetracarboxylic diimide.

Figure 11. 1,2,3,4,7,8,9,10-octa(n-butyl)-N,N'-di(n-octyl)-tetracene-5 of Example 3 of the present invention, 6: Absorption diagram of 11,12-tetracarboxylic diimide.

Figure 12. 1,2,3,4,7,8,9,10-octa(n-butyl)-N,N'-di(n-octyl)-tetracene-5 of Example 3 of the present invention, 6: Electrochemical diagram of 11,12-tetracarboxylic diimide.

Figure 13. 5,8,13,16-tetra(ethyl)-1,2,3,4,9,10,11,12-octahydrocyclohexane-N,N'- of Example 4 of the present invention The mass spectrum of bis(n-octyl)-tetracene-5,6:11,12-tetracarboxylic acid diimide.

Figure 14. 5,8,13,16-tetra(ethyl)-1,2,3,4,9,10,11,12-octahydrocyclohexane-N,N'- of Example 4 of the present invention ¹ H-NMR chart of bis(n-octyl)-tetracene-5,6:11,12-tetracarboxylic diimide.

Figure 15. 5,8,13,16-tetra(ethyl)-1,2,3,4,9,10,11,12-octahydrocyclohexane-N,N'- of Example 4 of the present invention Absorption pattern of bis(n-octyl)-tetracene-5,6:11,12-tetracarboxylic diimide.

Figure 16. 5,8,13,16-tetra(ethyl)-1,2,3,4,9,10,11,12-octahydrocyclohexane-N,N'- of Example 4 of the present invention Electrochemical diagram of bis(n-octyl)-tetracene-5,6:11,12-tetracarboxylic acid diimide.

Figure 17. 5,8,13,16-tetra(ethyl)-1,2,3,4,9,10,11,12-octahydrocyclohexane-N,N'- of Example 5 of the present invention Mass spectrum of bis(2,2,3,3,4,4,4-heptafluoro-n-butyl)-tetracene-5,6:11,12-tetracarboxylic acid imide.

Figure 18. 5,8,13,16-tetra(ethyl)-1,2,3,4,9,10,11,12-octahydrocyclohexane-N,N'- of Example 5 of the present invention ¹ H-NMR chart of bis(2,2,3,3,4,4,4-heptafluoro-n-butyl)-tetracene-5,6:11,12-tetracarboxylic acid imide.

Figure 19. 5,8,13,16-tetra(ethyl)-1,2,3,4,9,10,11,12-octahydrocyclohexane-N,N'- of Example 5 of the present invention Absorption pattern of bis(2,2,3,3,4,4,4-heptafluoro-n-butyl)-tetracene-5,6:11,12-tetracarboxylic acid imide.

Figure 20. 5,8,13,16-tetra(ethyl)-1,2,3,4,9,10,11,12-octahydrocyclohexane-N,N'- of Example 5 of the present invention Electrochemical diagram of bis(2,2,3,3,4,4,4-heptafluoro-n-butyl)-tetracene-5,6:11,12-tetracarboxylic acid diimide.

Detailed ways

Example 1; 1,2,3,4,7,8,9,10-octa(ethyl)-N,N'-bis(n-octyl)-tetracene-5 of Example 1 of the present invention, 6: 11,12-tetracarboxylic diimide.

Concrete synthetic steps are:

1. Add 20ml of freshly distilled tetrahydrofuran to 1mmol of zirconocene dichloride, and place the solution at -78°C under the protection of nitrogen gas;

2. Add 2 mmol of n-butyllithium dropwise to the mixture in step 1, and react for 60 minutes;

3. After 60 minutes, add 2 mmol of 3-hexyne to the mixture prepared in step 2, and react at room temperature for 2 hours;

4. After the reaction is over, remove 10 ml of tetrahydrofuran under vacuum and low temperature, and then add 300 mg of 2,3:6,7-tetrabromo-N, N'-di(n-octyl)-naphthalene-5, 6: 11,12-tetracarboxylic diimide, 200 mg cuprous chloride, under nitrogen protection, react at 50°C for 4 h. The product is extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, below 50°C The solvent was evaporated to dryness, and the products 1,2,3,4,7,8,9,10-octa(ethyl)-N,N'-bis(n-octyl)-tetracene-5 were obtained by silica gel column chromatography ,6:11,12-tetracarboxylic diimide 165 mg, the yield was 55%. Dark red powder, MS(MALDI-TOF,m/z): 814.6. Anal.Calcd for: C ₅₄ H ₇₄ O ₂ N ₄ (molecular weight: 814.6 ); ¹ H-NMR(CDCl ₃ ,400MHZ): δ = 4.27 (m, 4H), 3.02-3.07 (m, 8H), 2.86-2.87 (m, 8H), 1.82-1.86 (m, 4H), 1.47-1.49 (m, 4H), 1.28-1.36 (m, 28H) ,0.79-0.87 (m, 18H).

1,2,3,4,7,8,9,10-octa(ethyl)-N,N'-di(n-octyl)-tetracene-5,6:11,12-tetracarboxylic acid di Figure 1 shows the mass spectrum of the imide; Figure 2 shows the ¹ H-NMR chart; Figure 3 shows the ultraviolet-visible absorption chart; Figure 4 shows the electrochemical chart.

Example 2; 1,2,3,4,7,8,9,10-octa(ethyl)-N,N'-di(2,2,3,3,4,4,4-heptafluoro-n- Butyl)-tetracene-5,6:11,12-tetracarboxylic acid diimide.

Concrete synthetic steps are:

1. Add 20ml of freshly distilled tetrahydrofuran to 1mmol of zirconocene dichloride, and place the solution at -78°C under the protection of nitrogen gas;

2. Add 2 mmol of n-butyllithium dropwise to the mixture in step 1, and react for 60 minutes;

3. After 60 minutes, add 2 mmol of 3-hexyne to the mixture prepared in step 2, and react at room temperature for 2 hours;

4. After the reaction, 10 ml of tetrahydrofuran was sucked away under vacuum and low temperature, and 300 mg of 2,3:6,7-tetrabromo-N,N'-bis(2,2,3,3,4 ,4,4-heptafluoro-n-butyl)-naphthalene-5,6:11,12-tetracarboxylic acid diimide, 200 mg cuprous chloride, under nitrogen protection, react at 50 for 4 h. Extracted with methyl chloride, dried over anhydrous sodium sulfate, filtered, evaporated to dryness below 60°C, and separated by silica gel column chromatography to obtain products 1,2,3,4,7,8,9,10-octa(ethyl)-N, N'-bis(2,2,3,3,4,4,4-heptafluoro-n-butyl)-tetracene-5,6:11,12-tetracarboxylic acid diimide 132mg, the yield is 44%. Dark red powder, MS(MALDI-TOF,m/z): 954.5. Anal.Calcd for: C ₄₆ H ₄₄ F ₁₄ N ₂ O ₄ (molecular weight: 954.3); ¹ H-NMR (CDCl ₃ , 400 MHZ): δ = 5.07 (m, 4H), 2.87-3.01 (m, 16H), 1.26-1.34 (m, 12H), 0.81-0.84 (m, 12H).

1,2,3,4,7,8,9,10-octa(ethyl)-N,N'-bis(2,2,3,3,4,4,4-heptafluoro-n-butyl)- The mass spectrogram of naphthacene-5,6:11,12-tetracarboxylic diimide is shown in Figure 5; ^{the 1} H-NMR chart is shown in Figure 6; the UV-visible absorption chart is shown in Figure 7; The chemical map is shown in Figure 8.

Example 3; (1,2,3,4,7,8,9,10-octa(n-butyl)-N,N'-bis(n-octyl)-tetracene-5,6:11, 12-tetracarboxylic diimide)

Concrete synthetic steps are:

1. Add 20ml of freshly distilled tetrahydrofuran to 1mmol of zirconocene dichloride, and place the solution at -78°C under the protection of nitrogen gas;

2. Add 2 mmol of n-butyllithium dropwise to the mixture in step 1, and react for 60 minutes;

3. After 60 minutes, add 2 mmol of 5-decyne to the mixture prepared in step 2, and react at room temperature for 2 hours;

4. After the reaction is over, remove 10 ml of tetrahydrofuran under vacuum and low temperature, and then add 300 mg of 2,3:6,7-tetrabromo-N,N'-bis(n-octyl)-naphthalene-5, 6: 11,12-tetracarboxylic diimide, 200 mg cuprous chloride, under nitrogen protection, react at 55°C for 4 h. The product is extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, below 60°C The solvent was evaporated to dryness, and the products 1,2,3,4,7,8,9,10-octa(n-butyl)-N,N'-di(n-octyl)-tetracene- 5,6:11,12-Tetracarboxylic diimide 210mg, yield 52%. Dark red powder, MS(MALDI-TOF,m/z):1038.9. Anal.Calcd for: C ₇₀ H ₁₀₆ N ₂ O ₄ (molecular weight, 1038.8 ); ¹ H-NMR (CDCl ₃ ,400MHZ): δ = 4.24 (m, 4H), 2.98-3.02 (m, 8H), 2.72-2.75 (m, 8H), 1.75-1.84 (m, 12H), 1.50-1.60 (m, 12H), 1.29-1.38 (m, 128H) , 1.04-1.07(m, 28H), 0.86-0.90 (m, 6H), 0.67-0.70 (m, 12H).

1,2,3,4,7,8,9,10 – octa(n-butyl)-N,N'-di(n-octyl)-tetracene-5,6:11,12-tetracarboxylic acid The mass spectrogram of the imide is shown in Figure 9; ^{the 1} H-NMR chart is shown in Figure 10; the ultraviolet-visible absorption chart is shown in Figure 11; the electrochemical chart is shown in Figure 12.

Example 4 (5,8,13,16-tetra(ethyl)-1,2,3,4,9,10,11,12-octahydrocyclohexane-N,N'-bis(n-octyl )-tetracene-5,6:11,12-tetracarboxylic acid diimide)

Concrete synthetic steps are:

1. Add 20ml of freshly distilled tetrahydrofuran to 1mmol of zirconocene dichloride, and place the solution at -78°C under the protection of nitrogen gas;

2. Add 2 mmol of n-butyllithium dropwise to the mixture in step 1, and react for 60 minutes;

3. After 60 minutes, add 1 mmol of 3, 9-dodedecyne to the mixture prepared in step 2, and react at room temperature for 3 hours;

4. After the reaction is over, remove 10 ml of tetrahydrofuran under vacuum and low temperature, and then add 300 mg of 2,3:6,7-tetrabromo-N,N'-bis(n-octyl)-naphthalene-5, 6: 11,12-tetracarboxylic diimide, 200 mg cuprous chloride, under nitrogen protection, react at 55°C for 4 h. The product is extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, below 60°C The solvent was evaporated to dryness, and the product 5,8,13,16-tetra(ethyl)-1,2,3,4,9,10,11,12-octahydrocyclohexane-N,N was separated by silica gel column chromatography '-bis(n-octyl)-tetracene-5,6:11,12-tetracarboxylic acid diimide 144 mg, yield 48%. Dark red powder, MS(MALDI-TOF,m/z): 810.6 . Anal.Calcd for: C ₅₄ H ₇₀ N ₂ O ₄ (molecular weight: 810.5); ¹ H-NMR(CDCl ₃ ,400MHZ): δ = 4.27 (m, 4H), 2.98 (m, 16H), 1.94 (m, 8H), 1.83 (m, 4H), 1.27-1.37 (m, 20H), 0.83-0.86(m, 18H).

5,8,13,16-tetra(ethyl)-1,2,3,4,9,10,11,12-octahydrocyclohexane-N,N'-di(n-octyl)-naphthalene The mass spectrogram of benzene-5,6:11,12-tetracarboxylic diimide is shown in Figure 13; ^{the 1} H-NMR chart is shown in Figure 14; the UV-visible absorption chart is shown in Figure 15; the electrochemical chart is shown in 16.

Example 5; (5,8,13,16-tetra(ethyl)-1,2,3,4,9,10,11,12-octahydrocyclohexane-N,N'-di(2, 2,3,3,4,4,4-heptafluoro-n-butyl)-tetracene-5,6:11,12-tetracarboxylic diimide)

Concrete synthetic steps are:

1. Add 20ml of freshly distilled tetrahydrofuran to 1mmol of zirconocene dichloride, and place the solution at -78°C under the protection of nitrogen gas;

2. Add 2 mmol of n-butyllithium dropwise to the mixture in step 1, and react for 60 minutes;

3. After 60 minutes, add 1 mmol of 3, 9-dodedecyne to the mixture prepared in step 2, and react at room temperature for 3 hours;

4. After the reaction, 10 ml of tetrahydrofuran was sucked away under vacuum and low temperature, and 300 mg of 2,3:6,7-tetrabromo-N,N'-bis(2,2,3,3,4 ,4,4-heptafluoro-n-butyl)-naphthalene-5,6:11,12-tetracarboxylic acid diimide, 200 mg cuprous chloride, under nitrogen protection, reacted at 55°C for 4 h. Extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, evaporated to dryness below 60°C, and separated by silica gel column chromatography to obtain products 5, 8, 13, 16-tetra(ethyl)-1,2,3,4,9 ,10,11,12-Octahydrocyclohexane-N,N'-bis(N,N'-bis(2,2,3,3,4,4,4-heptafluoro-n-butyl)-naphthalene Benzene-5,6:11,12-tetracarboxylic acid diimide 105mg, yield 35%. Dark red powder, MS(MALDI-TOF,m/z): 950.4 . Anal.Calcd for: C ₅₄ H ₇₀ N ₂ O ₄ (molecular weight: 950.3); ¹ H-NMR (CDCl ₃ , 400MHZ): δ = 5.08 (m, 4H), 2.95-2.94 (m, 16H), 1.94 (m, 8H), 0.87-0.83 (m, 12H).

5,8,13,16–tetra(ethyl)-1,2,3,4,9,10,11,12-octahydrocyclohexane-(N,N'-bis(2,2,3, The mass spectrum of 3,4,4,4-heptafluoro-n-butyl)-tetracene-5,6:11,12-tetracarboxylic acid diimide is shown in Figure 17; ^{the 1} H-NMR chart is shown in Figure 17 18; the UV-visible absorption is shown in Figure 19; the electrochemical diagram is shown in 20.

Claims (21)

1. Naphthacene-5,6:11,12-tetracarboxylic acid diimide compound, which has the following formula I structure:

in: R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ , the same or different, independently represent hydrogen, substituted or unsubstituted, C1-30 Alkyl, C1-30 alkoxy, C3-30 cycloalkyl, C5-30 aryl, C1-30 alkylaryl, C1-30 alkyl heteroaryl, C1-30 alkyl heterocyclic, C1 -30 alkyleneoxyalkyl, C1-30 alkyleneoxyaryl, C1-30 alkyleneoxyheteroaryl, C1-30 alkyleneoxyheterocyclic, Wherein, optionally, _R3 and _R4 form together, substituted or unsubstituted, C3-30 cycloalkyl, C5-30 aryl, C1-30 alkylaryl, C1-30 alkylheteroaryl , C1-30 alkylene heterocyclic group, C1-30 alkylene oxyaryl group, C1-30 alkylene oxyheteroaryl group, C1-30 alkylene oxyheterocyclic group, Wherein, optionally, R ₈ and R ₉ form together, substituted or unsubstituted, C3-30 cycloalkyl, C5-30 aryl, C1-30 alkylaryl, C1-30 alkylheteroaryl , C1-30 alkylene heterocyclic group, C1-30 alkylene oxyaryl group, C1-30 alkylene oxyheteroaryl group, C1-30 alkylene oxyheterocyclic group, Provided that R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₈ , R ₉ and R ₁₀ are not simultaneously hydrogen. 2. The compound as claimed in claim 1, wherein R ₃ and R ₄ form together, or R ₈ and R ₉ form together, the following groups: substituted or unsubstituted, C3-30 cycloalkyl, C5-30 Aryl, C1-30 alkylaryl, C1-30 alkylheteroaryl, C1-30 alkylheterocyclyl, C1-30 alkyleneoxyaryl, C1-30 alkyleneoxyheteroaryl Group, C1-30 alkyleneoxyheterocyclic group. 3. The compound as claimed in claim 1 or 2, wherein aryl is selected from, substituted or unsubstituted, phenyl, naphthyl, anthracenyl, phenanthrenyl, naphthacene, pentaphenyl, hexacene Base, pyrenyl, indenyl, biphenyl, fluorenyl. 4. The compound according to any one of claims 1-3, wherein the heterocyclic group is selected from, substituted or unsubstituted, thienyl, furyl, pyranyl, phen

Thiyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, indolyl, isoindolyl, indazolyl, purinyl, quinozine Base, quinolinyl, phthalazinyl, naphthyridinyl, quinoxalinyl, pteridinyl, carbazolyl, carbalinyl, phenanthridinyl, phenanthrolinyl, acridinyl, phenazinyl, thiazolyl , phenothiazinyl, Azolyl, phen

Azinyl,

Azolyl, Diazolyl, furazanyl, dithienopyrrolyl, trithienyl, benzo

Azolyl, benzimidazolyl, benzothienyl, benzothiazolyl, benzothienyl, benzofuryl, benzopyranyl, benzophene

Thiyl, benzopyrrolyl, benzoimidazolyl, benzopyrazolyl, benzopyridyl, benzopyrazinyl, benzopyrimidinyl, benzopyridazinyl, benzoindolizinyl, benzoin Indolyl, benzoindazolyl, benzopurinyl, benzoquinazinyl, benzoquinolinyl, benzophthalazinyl, benzonaphthyridinyl, benzoquinoxalinyl, benzopteridinyl , benzocarbazolyl, benzocarbolinyl, benzophenanthridinyl, benzophenanthrolinyl, benzoacridinyl, benzophenazinyl, benzothiazolyl, benzophenothiazinyl, Benzo

Azolyl, benzophene

An azinyl group, or a group derived from ring fusion of the above-mentioned group and an aryl group as defined in claim 2 above, or a combination of the above-mentioned groups, each of these substituents may be additionally substituted. 5. The compound according to any one of claims 1-4, wherein the alkyl group is selected from, substituted or unsubstituted methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl Base, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl Alkyl, hexadecanyl, heptadecanyl, octadecyl, nonadecanyl and eicosyl. 6. The compound according to any one of claims 1-5, wherein the alkoxy group is selected from the group consisting of substituted or unsubstituted methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecane Oxygen, Tridecyloxy, Tetradecyloxy, Pentadecyloxy, Hexadecanyloxy, Heptadecanyloxy, Octadecanyloxy, Nonadecanyloxy group and eicosyloxy group. 7. The compound according to any one of claims 1-6, wherein the alkylene group is selected from the group consisting of substituted or unsubstituted methylene, ethylene, propylene, isopropylidene, n-butylene, S-butylene, isobutylene, tert-butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecylene, nonadecanyl and eicosanylene. 8. The compound according to any one of claims 1-7, wherein the cycloalkyl group is selected from the group consisting of substituted or unsubstituted cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl , Cyclodecyl, Undecylcycloalkyl, Dodecylcycloalkyl, Tridecylcycloalkyl, Tetradecylcycloalkyl, Pentadecylcycloalkyl, Hexadecylcycloalkyl, Heptadecan Cycloalkyl, Octadecylcycloalkyl, Nadecacycloalkyl and Eicoscycloalkyl. 9. The compound according to any one of claims 1-8, wherein heteroaryl is selected from, substituted or unsubstituted, pyrrolyl, pyrazinyl, pyridyl, indolyl, isoindolyl, furyl , benzofuryl, , isobenzofuryl, quinolinyl, 1-isoquinolyl, quinoxalinyl, carbazolyl, phenanthridinyl, acridinyl, o-phenanthrenyl, phenazine base, phenothiazinyl, phenothiazinyl, phen

Azinyl, Azolyl, furanyl, thienyl. 10. The compound according to any one of claims 1-9, wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different, Each independently represents a halogenated C1-30 alkyl group, preferably a perhalogenated C1-30 alkyl group, which is preferably substituted by fluorine, chlorine, bromine, or iodine. 11. The compound according to any one of claims 1-10, wherein the substituent is selected from: - alkyl, which has 1-16 carbon atoms, - alkoxy, which has 1-16 carbon atoms, - aryl, which has 5-16 carbon atoms, - cycloalkyl, which has 3-16 carbon atoms, - a heterocyclic group having 5-16 carbon atoms, the heteroatom T group contained in the group is selected from B, Si, Sn, N, O, S and Se; - heteroaryl, which has 1-16 carbon atoms, - Aralkyl groups having 5-16 carbon atoms, wherein the alkyl moiety has 1-16 carbon atoms. 12. The compound as claimed in claim 11, said substituent is selected from: - Alkyl groups such as methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl ; - Cycloalkyl, such as cyclopropyl, cyclopentyl, or cyclohexyl; - Alkenyl, such as vinyl, allyl, 2-butenyl, or 3-pentenyl; - alkynyl, such as propargyl or 3-pentynyl, - aryl groups such as phenyl, p-methylphenyl, naphthyl or anthracenyl; - Amino groups, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, or xylylamino; - alkoxy, such as methoxy, ethoxy, butoxy or 2-ethylhexyloxy; - Aryloxy, such as phenyloxy, 1-naphthyloxy, or 2-naphthyloxy; - heteroaryloxy, such as pyridyloxy, pyrazolyloxy, pyrimidinyloxy or quinolinyloxy; - Acyl groups such as acetyl, benzoyl, formyl or pivaloyl; - alkoxycarbonyl, such as methoxycarbonyl or ethoxycarbonyl; - aryloxycarbonyl, such as phenyloxycarbonyl; - acyloxy groups such as acetoxy or benzoyloxy; - amido groups such as acetamido or benzoylamino; - alkoxycarbonylamino, such as methoxycarbonylamino; - aryloxyoxyamino, such as phenyloxycarbonylamino; - Sulfonylamino, such as methanesulfonylamino or benzenesulfonylamino; - sulfamoyl, such as aminosulfonyl, methylsulfamoyl, dimethylsulfamoyl, or phenylsulfamoyl; - carbamoyl, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, or phenylcarbamoyl; - Alkylthio, such as methylthio or ethylthio; - Arylthio, such as phenylthio; - Heteroarylthio, such as pyridylthio, 2-benzimidazolylthio, 2-benzo Azolylthio, or 2-benzothiazolylthio; - Sulfonyl, such as methylsulfonyl or toluenesulfonyl; - sulfinyl groups such as methylsulfinyl or phenylsulfinyl; - ureido, such as ureido, methylureido or phenylureido; - Phosphate amides, such as diethylphosphoramide or phenylphosphoramide; - Hydroxyl; - mercapto; - Halogen atom (such as fluorine atom, chlorine atom, bromine atom, or iodine atom); - cyano; - sulfo group; - Carboxyl; - Nitro; - Hydroxamic acid group; - sulfinyl group; - hydrazino; - imino; - Heterocyclic groups such as imidazolyl, pyridyl, quinolinyl, furyl, thienyl, piperidyl, morpholino, benzo

Azolyl, benzimidazolyl, and benzothiazolyl; - Silyl groups such as trimethylsilyl or triphenylsilyl. 13. The compound according to any one of claims 1-12, which are:

,

,

or

, Wherein Et represents ethyl, and Bu represents butyl. 14. The method for preparing the compound described in any one of claims 1-13, which comprises the steps of: 1). Reaction of the halogenated metallocene reagent Cp ₂ LX ₂ with the alkyne compound B to obtain the compound of formula II and/or formula III:

and / or

in, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different, Definitions as defined in any one of claims 1-13, Cp represents cyclopentadienyl or known as cyclopentadienyl, L represents the IVA or IVB group metals in the periodic table of elements, such as zirconium or titanium, X represents halogen, such as fluorine, chlorine, bromine, iodine, B represents an alkyne compound, such as R≡R', RC≡C-(CH ₂ ) _n -C≡C-R'', or RC≡C-(CH ₂ ) _n -C≡C-(CH ₂ ) _n - C≡C-R''', wherein R, R', R'' and R''', the same or different, represent a group as defined in any one of claims 1-13 or a suitable protecting group , such as trihydrocarbylsilyl such as trimethylsilyl, triisopropylsilyl or triphenylsilyl, or aryl such as phenyl; n=3,4,5,6,7,8,9 or 10 ; 2). The compound of formula IV tetrahalogenated tetracarboxylic naphthalene diimide reacts with the compound of formula II and or formula III obtained in the previous step to obtain the compound of formula I:

in, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different, Definitions as defined in any one of claims 1-13, X, same or different, represents halogen, such as fluorine, chlorine, bromine, iodine. 15. The method according to claim 14, wherein, in step 1), a solvent is added to the compound of formula VI, and the ratio of the compound of formula VI to the solvent is 0.01-1.0 mmol/ml. 16. The method according to claim 14 or 15, wherein the molar ratio of the tetrahalogenated tetracarboxylic naphthalene diimide compound to the compound of formula VI is 1:1-10. 17. The method according to any one of claims 14-16, wherein a catalyst is added to the product of step 1), and the molar ratio of the catalyst to the tetrahalogenated tetracarboxylic naphthalene diimide compound is 10:1-1. 18. The method according to any one of claims 14-17, wherein the reaction temperature is controlled at 0°C to 70°C. 19. The method according to claim 17 or 18, wherein the catalyst is cuprous chloride. 20. The application of the compound according to any one of claims 1-13 as a light-absorbing material and an electron-transporting material in organic electroluminescent devices, organic thermochromic elements, organic field-effect transistors, and organic solar cells. 21. An organic electroluminescent device, an organic thermochromic element, an organic field effect transistor or an organic solar cell, comprising the compound according to any one of claims 1-13.

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